CHEMISTRY

NMDCAT
Lecture # 13
(Liquids and Solids)
Liquids:
1. Properties of liquids
2. Difference between Intramolecular and Intermolecular Forces
3. Type of Intermolecular Forces
(a) Dipole - Dipole Forces (b) Ion Dipole Forces
(c) Debye Forces (d) London Dispersion Forces
(e) Hydrogen Bonding and its applications
(i) Describe the hydrogen bonding in H2O, NH3
and HF molecules.
(ii) Anomalous behaviour of water when its density
shows maximum at 4oC
4. Vapor pressure
5. Boiling point and external pressure
 1. Properties of Liquids
MCQ: Which of the following properties is not shown by liquids

(A) They have the ability to flow

(B) They have the ability to evaporate at all temperatures
(C) They can not be compressed even at high pressure slightly
(D) They can diffuse into one another
Answer Explanation (C)
It is incorrect statement
The correct statement is as follow:
• Liquids are generally incompressible due to negligible
intermolecular spaces
• But at very high pressure they can be compressed slightly
 2. Intermolecular Forces
Type of attractive forces
(I) Intramolecular forces (II) Intermolecular forces
Intramolecular Forces Intermolecular Forces
 T he attracti ve forces w hic h exist between atoms /ions  The attracti ve fo rces whi c he xist betwe e ni ndi vi dual particles
within a substance are called intramolecular forces. are called intermolecular forces.
e.g. co va lent bond , ionic bond , coordinate co va lent bond e .g. dipole -dipole fo rces , dipole -i ndu ce d dipole fo rces , io n-
are intramolecular forces. di pole fo rces , Lo ndo n dispersio n fo rces a nd hydr o ge n bo ndi ng
are intermolecular forces.
 They are stronger forces  They are weaker forces
 They involve true chemical bonds  They involve additional forces
 They are shown by (+, ) () ()  They are shown by dotted lines (……)
 T he molecular s hapes , bond angles , bond energy and  The p hysical state a nd p hysical properties o f a subs ta nce
c hemical properties depend upon the strengt hof t hese depend upon the strength of these forces.
forces.
H 2O   H O g  ΔH = +40.7 kJmol -1
e.g. H 2O(g ) 
 H 2(g )  1 / 2O 2(g ) H  920 kJmol 1 2
e.g. H 2O   H 2O g  ΔH = +40.7 kJmol -1
 T his s hows t hat brea king of intramolecular forces  Thi s s ho w s t hat br ea ki ng o f i ntermolecular re quire lo w
er
require higher energy. energy.
3. Type of Intermolecular forces
(a) Dipole - Dipole Forces
(b) Ion Dipole Forces
(c) Debye Forces
(d) London Dispersion Forces
(e) Hydrogen Bonding
(a) Dipole - Dipole Forces
“The attractive force between the positive end of one polar
molecule and the negative end of another polar molecule is
called dipole-dipole forces.”

Explanation
When two polar molecules (having permanent dipoles) approach
each other, the positive end of one molecule is directed to the
negative end of the other molecule.
e.g. in HCl molecule both atoms differ in electronegativity (e.g.
H = 2.1 Cl = 3.0). Therefore, Cl-atom bears partial negative
charge () and H-atom bears partial positive charge (+). So
whenever these two polar molecules come close to each other,
then their opposite ends attract each other.

H   Cl    H  Cl
polar molecules polar molecules

Permanent Dipole DDF Permanent Dipole

Factors Affecting Dipole – Dipole Forces
The strength of dipole – dipole forces depend upon the following two
factors.
(i) The electronegativity difference between bonded atoms.
Greater is the electronegativity difference between two bonded atoms in
a polar molecule, stronger are the dipole-dipole forces
(ii) Distance between the molecules
Greater is the distance between the polar molecules, weaker are the
strength of dipole-dipole forces and vice versa
Effects of Dipole-Dipole Forces
The strength of these forces affect the physical properties of substances.
Greater the strength of these dipole – dipole forces, greater are the
values of thermodynamic parameters like melting points, boiling points,
Hf, Hv, Hsub, viscosity, surface tension etc. of substances.
(b) Ion Dipole Forces
An ion-dipole force is an attractive force that results from the
electrostatic attraction between an ion and a neutral molecule that
has a dipole.
e.g.
ion-dipole forces are the forces between sodium (Na+) and chlorine (Cl–)
and a polar water molecule (H2O). Here, the positively charged sodium ion
is attracted to the negatively charged oxygen (Oδ-) atom, and the
negatively charged chloride (Cl–) ion is attracted to the positively charged
hydrogen (Hδ+) atom as shown the diagram].
Characteristics of Ion Dipole Forces
Here are some facts and characteristics of the ion-dipole
forces which can be applied to determine it.
• The ions and dipoles are aligned closer to one another so that
the forces are maximum.
• Their strength is proportionate to ion charge or dipole
strength.
• They are stronger than the dipole-dipole forces
• They are weaker than the intramolecular ionic and covalent
• bonds.
Most commonly found in solutions. Especially important for
solutions of ionic compounds in polar liquids.
• A positive ion (cation) attracts the partially negative end of a
neutral polar molecule.
• A negative ion (anion) attracts the partially positive end of a
neutral polar molecule.
(c) Debye Forces (Dipole-induced dipole forcers)
A non-polar molecule may be polarized by the presence of a
polar molecule (dipole) near it, thereby making it an induced
dipole. The interactions between them are then called Dipole-
Induced Dipole Interactions. Their strength will depend upon
the strength of the dipole and the ease of polarizability of the
non-polar molecule.
e.g. Noble gases get polarized in the presence of polar
molecules as shown in figure below.
Dipole-induced dipole forces
 (d) Instantaneous Dipole–Induced Dipole Forces (London Dispersion Forces)

The momentary forces of attraction created between instantaneous

dipole and induced dipole are called dipole induced dipole interaction
or London dispersion forces.
Explanation
• Fritz London, a German physicist in 1930, gave a simple explanation for these weak attractive forces
between non-polar molecules.
• According to him, in helium gas, the electrons of one atom influence the moving electrons of other
atom. Electrons repel each other and they tend to stay as far apart as possible.
• When the electrons of on atom come close to the electrons of other atom, they are pushed away from
each other.
• In this way a temporary dipole is created in the atom as shown in the fig.
 • The result is that, at any moment, the electron density of the atom is no more
symmetrical. It has more negative charge on one side than on the other.
• At that particular instant, the helium atom becomes a dipole. This is called
instantaneous dipole. Thus in this way instantaneous dipole-induced dipole
forces develop between atoms or molecules.
Characteristic Features of London Dispersion Forces
• They are very short-lived forces of attraction because the electrons
keep moving
• They are temporary forces
• They are short range forces
• They are the weakest forces
• They are present in all type of molecules whether polar or non-polar.
• But they are very significant in non-polar molecules like Cl2, H2, CO2,
CH4, N2, C10H8 (naphthalene) and noble gases. He, Ne, Ar, etc.
 Evidence of London Dispersion Forces
• The change of inert gases into liquid or solid phase
• The Joule Thomson effect
• The non-ideality of real gases

Q: Which one of the following halogens has lowest boiling point?

(A) F2 (C) Cl2
(B) I2 (D) Br2
Answer Explanation
• F2 is a gas and it has the lowest boiling point because molecular
size is smaller
• Thus it has comparatively less polarizability in the molecules of
F2 and have weak London Dispersion Forces
Q: Which of the following factors affects strength of London Dispersion
forces?
(A) Size of electronic cloud of atoms or molecules only
(B) The number of atoms in a non-polar molecule only
(C) Both A and B
(D) None of these

Answer Explanation (C)

These forces depend upon the following two factors:
i. Size of electronic cloud of atoms or molecules
ii. The number of atoms in a non-polar molecules
 (e) Hydrogen Bonding
Hydrogen bonding is the electrostatic force of attraction
between a highly electronegative atom and partial positively
(+) charged hydrogen atom.
e.g. The more electronegative atoms which are responsible
for creating hydrogen bonding are fluorine, oxygen, nitrogen
and rarely chlorine. The strength of hydrogen bond is
generally twenty times less than that of covalent bond.
(i) Describe the hydrogen bonding in H2O, NH3 and HF molecules.
Hydrogen bonding in H2O, NH3 and HF respectively is shown below:
MCQ: Which of the following is correct order of boiling points of the given liquids?
A) H2O > HF > HCl > NH3 C) H2O > HF > NH3 > HCl
B) HF > H2O > HCl > NH3 D) HF > H2O > NH3 > HCl
ANSWER EXPLANATION: (C)
Formula Reason Boiling point
 I n wat er there are t wo B.P = 100oC
(H2O)
hydrogen bonds per molecule. (greater than the rest)
 I n HF t here is one hydrogen B.P = 19.5oC
(HF)
bond per molecule (less than water)
 I n NH3 there i s one hydr ogen B.P = -33.34oC
(NH3)
bond per molecule (less polar than HF)
 No hydrogen bonding B.P = -85oC
(HCl)  has dipole-dipole forces (DDF)
 DDF are weaker than H-bonds
 Applications of Hydrogen Bonding
• Hydrogen bonding affects the following physical properties:
• Strength of acids
• Solubility of hydrogen bonded molecules
• Cleansing action of soaps and detergents
• H-bonding in biological compounds
• H-bonding in paints and dyes
• Structure of ice
• Strength of acids:
• The strength of an acid depends upon the extent of its ionization.
• The low acidic strength of HF molecule as compared to HCl, HBr and
HI is due to the strong hydrogen bonding in HF molecules.
• As the partial positively charged hydrogen is entrapped between two
highly electronegative atoms, so this acid does not ionize completely
in water and hence HF becomes a weak acid.

F
  
H 120o H H
 
F F
 • Solubility of hydrogen bonded molecules
• Water is the best example of hydrogen bonded system. Ethyl alcohol
(C2H5OH) also has the tendency to form hydrogen bonds.
• So ethyl alcohol can dissolve in water because both can form
hydrogen bonds with each other.

• Carboxylic acids are soluble in water, if their sizes are

small. They form hydrogen bond with water molecules
and thus dissolve.
• Hydrocarbons are not soluble in water at all, because
they are non-polar compounds and there are no
chances of hydrogen bonding between water and
hydrocarbon molecules.
in ethanol and water
• Cleansing action of soaps and detergents
• The cleansing action of soaps and detergents is due to hydrogen
bonding.
• Reason is that polar parts of their molecules are water soluble
(hydrophilic) due to hydrogen bonding and the non-polar parts like
alkyl or benzyl portions are insoluble in water (hydrophobic).

• H-bonding in biological compounds

• Hydrogen bonding exists in the molecules of living system.
• Proteins are the important part of living organisms.
• Fibres like those found in the hair, silk and muscles consist of long
chains of amino acids.
• These long chains are coiled about one another in a spiral.
• This spiral is called a helix.
• Such a helix may either be right handed or left handed.
• H- bonding in proteins
In the case of right handed helix the groups like > NH
and > C = 0 are vertically adjacent to one another and
they are linked together by hydrogen bonds. These H-
bonds link one spiral to the other. X-rays analysis has
shown that on the average there are 27 amino acids
units for each turn of the helix.
• H-bonding in carbohydrates
T he food mat eri al s like car bohydrat es i ncl ude
gl ucose, fructose and sucr ose. T hey all hav e  OH
groups due to which hydrogen bonding is present.
• Hydrogen bonding in DNA
There are two spiral chains in DNA
(Deoxyribonucleic acid) which are coiled about
each other on a common axis. In this way, they
give a double helix. This is 18-20Å in diameter.
They are linked together by H-bonding between
their sub-units.
• H-bonding in paints and dyes
One of the most important properties of paints and dyes is their
adhesive action. This property is developed due to hydrogen bonding.
Similar type of hydrogen bonding makes glue and honey as sticky
substances.
Hydrogen bonding is very important in thread making materials like
cotton, silk and synthetic fibres for clothing. This hydrogen bonding is
responsible for their rigidity and the tensile strength.
• Structure of Ice:
• The molecules of water have tetrahedral structure. Two lone pairs of
electrons on oxygen atom occupy two corners of the tetrahedron. In
the liquid state, water molecules are extensively associated with each
other and these associations break and are reformed because the
molecules of water are mobile.
Density of ice
• When the temperature of water is decreased and ice is formed then
molecules become more regular and this regularity extends
throughout the whole structure. Empty spaces are created in the
structure. Thus when water freezes it occupies 9% more space and its
density decreases. The result is that ice floats on water.
Diamond like structure
• The structure of ice is just like that of a diamond because each atom
of carbon in diamond is at the centre of tetrahedron just like the
oxygen of water molecule in ice.
MCQ:
Which one of the following statements is incorrect about water and ice?
Opt. Water Ice
A. Hexagonal structure Tetrahedral structure
B. At 4oC water has maximum density At 0oC ice has lower density
C. At 4oC it has minimum volume At 0oC volume of ice increases 9%
D. It is in the liquid state It is in the solid state
 Answer Explanation: (A) It is incorrect statement.
The correct statement is as follow:
Opt. Water Ice
A. Water shows tetrahedral structure Ice shows hexagonal structure

Tetrahedral structure of water Hexagonal structure of ice

(Cage like structure of ice)
Q: Hyrdrogen bonding is unimportant in:
(A) DNA Structure
(B) Liquid HF
(C) The liquid property of water
(D) Liquid methane
Answer Explanation (D)
• Hydrogen bonding is unimportant in liquid methane
• Liquid methane has London dispersion forces
• Because it is non-polar molecule
Q: Acetone and cholorform are soluble in each other due to:
(A) Intermolecular hydrogen bonding (C) Ion dipole forces
(B) London Dispersion Force (D) All of above
Answer Explanation (A)
Acetone and cholorform are soluble in each other due to
Intermolecular hydrogen bonding
 Q: Identify the incorrect statement?
Options Properties Comments

A) Strength of acid HF is stronger acid than HCl due to H-bonding

B) Paints and dyes The adhesi ve nat ure of certain pai nts and dyes is due to H-
bonding
C) Food material Glucose and fructose are soluble in water due to H-bonding

D) DNA Double stranded structure of DNA has hydrogen bonding

Answer Explanation: (A) It is incorrect statement.

The correct statement is as follow:
Options Properties Comments
A) Strength of acid HF is weaker acid than HCl because HF has strong
H-bonding
 (ii) Anomalous behavior of water when its density
shows maximum at 4oC
MCQ: In anomalous expansion of water, at what temperature, the
density of water is maximum?
A) 4oC C) > 4oC
B) < 4oC D) 10oC
ANSWER EXPLANATION: (A)
 All the liquids expand on heating and contract on cooling but liquid water shows
anomalous behaviour. By decreasing temperature water shows maximum density at 4oC
but below this temperature instead of contraction water expands.
 That is why at 0oC rearrangement of water molecules take place and change into ice and
its volume increases 9%. It is because of this reason ice has less density than that of
water at 4oC and its floats on water.
 Water never has an absolute density because its density varies with temperature.
Water has its maximum density of 1g cm3 at 4oC.
 When temperature changes from either greater or less than 4oC, the density becomes
less than 1g cm3.
 33
4. Vapour Pressure (V.P)

Measurement of V.P
Definition Factors
Barometric Manometric
Th e vapour method method
pressure of a
It is not • The most
li quid is a
accurate accurate
pressure met hod method
exerted by the becaus e i n • Because ai r
Which affect Which do not
vapours of the thi s has been
V.P affect V.P
li quid in met hod ai r co mpl etel y
e quilibrium • Nature of liquid • Surface area has not re moved fro m
with the li quid • Size of molecule • Volume of the container been liquid
at a given • Intermolecular forces • Amount of liqu id in the re moved P = Pa + ∆h
temperature • Temperature container f or m t he
liquid
 Actually, the pressure on the surface Manometric method 34
of the li quid in the flask is e qual to the
sum of the atmospheric pressure and
the vapour pressure of li quid, and it is
given by the following equation:
P = Pa + ∆h
P = Vapour pressure of the li quid at
1atm pressure
Pa = atmospheric pressure Measurement of vapour pressure of
∆h = difference in the heights of the a liquid by manometric method
mercury levels in the two limbs of the
manometer.
Q: V a pour pressure (e quilibrium pressure ) of a li quid is that pressure which is exerted by the vapours
of the li quid in e quilibrium with the li quid at a given temperature. It depends on all of the following
factors EXCEPT:
A) Nature of liquid C) Temperature
B) Intermolecular forces D) Amount of liquid
Explanation: (D) Vapour pressure of a liquid does not depend on amount of liquid.
Q: Which of the following is the most accurate method to
measure vapour pressure of a liquid?
(A) Manometric method only
B) Barometric method only
C) Both barometric and manometric method
D) Difficult to predict

Answer Explanation (A)

• The most accurate method to measure vapour pressure of a
liquid is manometric method because in this method air has
been completely removed before measuring vapor pressure of
a liquid
 5. Boiling point
Definition
It is temperature at which internal Pressure cooker
vapour pressure of the liquid (B.P ∝ atmospheric pressure)
becomes equal to the external In pressure cooker boiling
atmospheric pressure. point is increased by
increasing external
atmospheric pressure. Since
more amount of heat is
absorbed by water, therefore
cooking becomes very quick
under increased external
pressure.
36
Applications
Vacuum Distillation
(B.P ∝ 1/vapour pressure)
The distillation process that is carried
out under reduced pressure or in
vacuum is called vacuum distillation.
It is economical. Glycerin
decomposes at its normal boiling
point, i.e. 290 o C at 760torr. It can
safely distill without decomposition
at 210 oC under reduced pressure of
50torr
 37

Q: Mark incorrect statement about boiling point of water:

A) Boiling point of water is 120oC at 1489 torr pressure
B) Boiling point of water is 25oC at 23.7 torr pressure
C) Boiling point of water is 98oC at 700 torr pressure at the top of Murree Hills
D) Boiling point of water is 70oC at 323 torr pressure at the top of Mount Everest

Explanation: (D) It is incorrect statement.

In fact, boiling point of water is 69oC at 323 torr pressure at the top of Mount Everest.
Q: What is the boiling point of water at a mountain?
(A) It is 100 oC
(B) It is < 100 oC since the atmospheric pressure is greater
(C) It is > 100 oC since the atmospheric pressure is greater
(D) It is < 100 oC since the atmospheric pressure is less

Answer Explanation (D)

• Boiling point of a liquid is directly related with
atmospheric pressure
• Greater is the atmospheric pressure, greater is the
boiling point of liquid and vice versa
• Due to this reason, boiling point of water at a mountain
is < 100 oC since the atmospheric pressure is less
Solids:
1. Introduction
2. Types of solids
3. Properties of Crystalline Solids
4. Types of Crystalline Solids
(a) Mettalic solids (b) Ionic solids
(c) Covalent solids (d) Molecular solids
5. Crstal Lattice
(a) Unit Cell (b) Types of Unit Cells
6. Lattice Energy
 1. Introduction
The solid state of matter is characterized by its
• Rigidity
• Hardness
• Definite Shape
• Definite Volume
• Mechanical Strength
 2. Types of Solids
(a) Crystalline Solids or True Solids
(b) Amorphous Solids

Property Crystalline solids Amorphous solids

Shape Definite characteristic Irregular shape
geometrical shape
Melting point Melt at a sharp and Gradually soften over a range
characteristic temperature of temperature.
Cleavage plane When cut with a sharp edged When cut with a sharp edged
tool, they cut into two pieces tool , they cut into two pieces
and the newly generated with irregular surfaces.
surfaces are plain and smooth.
 Property Crystalline solids Amorphous solids
Heat of fusion They have a definite and They do not have definite heat
characteristic heat of fusion. of fusion.
Anisotropy Anisotropic in nature Isotropic in nature.
Nature True solids Pseudo solids or super cooled
liquids or highly viscous liquids.
Examples NaCl, Sugar, Ice, Diamond etc. Rubber, Plastic, Glue, Glass,
Paper etc.
MCQ: Which one of the following characteristic features is not shown by
crystalline solids and amorphous solids?
Opt. Crystalline solids Amorphous solids
A) They have definite geometry T hey do not ha ve defini te
geometry
B) They have sharp melting points T hey do not ha ve sha rp melting
points
C) They show cleavage plan They do not show cleavage plan
D) They show isotropy They show anisotropy
 ANSWER EXPLANATION: (D)
It is incorrect statement
The correct statement is as follow:
Opt. Crystalline solids Amorphous solids
They show anisotropy They show isotropy
 Some of the crystals show  Some of the solid substances do
variation in physical properties not show variation in physical
depending upon the direction. properties by changing in the
D)
Such properties are called direction. Such properties are
anisotropic properties and the called isotropic properties and
phenomenon is referred to as the phenomenon is referred to
anisotropy. as isotropic.
 3. Properties of Crystalline Solids
(1) Geometrical Shape
All the crystalline solids have a definite distinctive geometrical shape
due to definite and orderly arrangement of atoms, ions or molecules in
three dimensional space. For a given crystal, the interfacial angles, at which
the surfaces intersect are always the same no matter in which shape they
are grown. The faces and angles remain characteristic even when the
material is ground to a fine powder.
(2) Melting Points
Crystalline solids have sharp melting points and can be identified from
their definite melting points.
(3) Cleavage Planes
Whenever the crystalline solids are broken they do so along definite
planes. These planes are called the cleavage planes. They are inclined to one
another at a particular angle for a given crystalline solid. The value of this
angle varies from one solid to another solid.
(4) Anisotropy
“The phenomenon in which a crystalline solid shows variation in
certain physical properties depending upon the direction is
called anisotropy.”
Anisotropic properties:
Anisotropic properties are:
• Refractive index.
• Thermal and electrical conductivities.
• Co-efficient of thermal expansion.
• Cleavage planes.
Reason
The variation in anisotropic properties with direction is due to the fact that
the orderly arrangement of particles in crystalline solids is different in
different directions.
In figure,
From A  B = same kind of particles in this direction
C  B = different kind of particles in this direction
Examples
i. E lectri cal conductiv ity of graphi te is greater i n one di recti on t han i n
anot her. Actuall y, el ectrons i n graphi te are mobil e for el ectri cal
conducti on parall el to the l ayers onl y. T heref ore, its conductiv ity i n thi s
direction is far better than perpendicular to the other direction.
ii. Cleavage itself is anisotropic behaviour.
(5) Symmetry
“T he repetition of angl es, edges or faces when a crystal is rotated about 36 0
along its axis is called symmetry.”
Symmetry elements
Following are the symmetry elements of a crystal:
(i) Plane of symmetry.
(ii) Axis of symmetry.
(iii) Centre of symmetry.
(6) Habit of a Crystal
“The shape of a crystal in which it usually grows is called habit of a crystal.”
Preparation
A crystal can be prepared:
(i) By moderate cooling of a saturated solution.
(ii) By slow cooling of a liquid.
These are formed by growing in various directions.
Change in habit of a crystal
If the condi tions f or growi ng a crystal are mai ntai ned, then t he shape of the
crystal al ways re mai ns the sa me. If the condi ti ons are changed, the shape of
the crystal may change.
For exa mpl e, a cubi c crystal of NaCl beco mes needl e li ke when 10% urea is
present in its solution as an impurity.
(7) Isomorphism
“T he phenomenon i n whi ch t wo different substances exi st i n the sa me
crystalline form is called isomorphism.”
Isomorphs
“T hose crystalli ne substances whi ch hav e sa me crystalli ne f or mar e i somor phs
to each other.”
• Isomorphs may be compounds or elements.
Examples:
Isomorphs Crystalline Form Atomic Ratio
NaNO3, KNO3 Rhombohedral 1:1:3
K2SO4, K2CrO4 Orthorhombic 2:1:4
ZnSO4, NiSO4 Orthorhombic 1:1:4
NaF, MgO Cubic 1:1
Cu, Ag Cubic 1:1
Zn, Cd Hexagonal 1:1
 Similarities and dissimilarities of isomorphs
Similarities Dissimilarities
crystalline form physical properties
atomic ratio chemical properties
way of combination nature of atoms
number of atoms
structure of anions
(8) Polymorphism
“T he phenomenon i n whi ch a compound exi sts in mor e t han one crystalline
forms is called polymorphism.”
Polymorphs
“T he compound whi ch exi sts i n more t han one crystalli ne for ms i s call ed
polymorphic compound and these forms are polymorphs of each other.”
Example:
Substance Crystalline Forms
AgNO3 Rhombohedral and orthorhombic
CaCO3 Trigonal and orthorhombic
Important points
• It is a compound phenomenon.
• Polymorphs have same chemical properties.
• Polymorphs have different physical properties due to the different structural
arrangement of their particles.
(9) Allotropy
“T he phenomenon i n whi ch an el ement exi sts i n mor e t han one crystalli ne
for ms i s call ed all otropy and these f orms of the ele ment are call ed all otropes
or allotropic forms.”
Examples
Element Allotropic Forms
Sulphur, S Rhombic, monoclinic
Carbon, C Cubic (diamond), hexagonal (graphite)
Tin, Sn Grey tin (cubic), white tin (tetragonal)
Important points
It is an elemental phenomenon.
Allotropes of an element have same chemical but different physical properties.
(10) Transition Temperature
“T he te mperat ure at whi ch t wo crystalli ne f or ms of the sa me substance can co-
exist in equilibrium with each other is called transition temperature.”
Examples

Important points
At transition temperature, one crystalline form of a substance changes to another.
Above and below this temperature, only one form exists.
Th e transition temperature of allotropic forms of an element is always less than its
melting point.
MCQ: Those solids in which atoms, ions or molecules are arranged in
a definite three-dimensional pattern are called crystalline solids.
Identify the incorrect statement about crystalline solids:
A) They have sharp melting points
B) They show only centre of symmetry
C) They show anisotropy
D) They have cleavage planes
ANSWER EXPLANATION: (B)
It is incorrect statement
The correct statement is as follow:
• The repetition of faces, angles or edges when a crystal is rotated by
360o along its axis is called symmetry.
• This is important property of the crystal and there are various
types of symmetry elements found in crystal like, center of
symmetry, plane of symmetry and axis of symmetry.
1. CENTER OF SYMMETRY:
A centre of sy mmetry exists i n a crystal if an i magi nary li ne can be extended
from any poi nt on its surface thr ough its centre and a si mil ar poi nt is present
along the line equidistant from the centre. This is equivalent to 1, or inversion.

2. PLANE OF SYMMETRY
A plane through a crystal that divides the crystal into two parts that are mirror
images of each other.
3. AXIS OF SYMMETRY
An axi s of sy mmetry or axi s of rotati on i s an i magi nary line, passi ng
thr ough the crystal such that when t he crystal is rot at ed about thi s li ne, it
pr esents the sa me appearance mor e than once i n one co mpl et e rev ol uti on
i.e., in a rotation through 360°.
Q: The isomorphic substances have:
A) Same geometry C) Both A and B
B) Same atomic ratio D) None of the above
Answer Explanation: (C)
The isomorphic substances have same geometry and same atomic ratio
Isomorphs Atomic ratio Crystal substance
NaCl and MgO 1:1 Cubic
KNO3 and NaNO3 1:1:3 Rhombohedral
Zn and Cd 1:1 Hexagonal
KNO3 and CaCO3 1:1:3 Rhombohedral
MCQ: Which one of the following is a crystalline solid:
A) Glass C) Rubber
B) Plastic D) Diamond
ANSWER EXPLANATION: (D)
Diamond shows the following properties:
 Covalent solid
 Colourless
 Involves sp3 orbital hybridization
 Non-conductor
 Shows face centered cubic structure
 Three dimensional
 The refractive index of a diamond is 2.419. A diamond is known to have the
highest amongst all natural minerals. The refractive index is measured by n =
c/v, where n = refractive index, c = speed of light, and v = velocity of light
through the material. The index of refraction of diamond is 2.4175. It has high
refractive index value
The temperature at which one crystalline form of a substance
changes into another form is called:
A) Transition temperature C) Critical temperature
B) Absolute temperature D) Optimum temperature
Answer Explanation: (A)
Transition temperature of some substances are shown below:
Suplhur  S8 
95.5o C
 Sulphur S8
 Rhombic   Monoclinic 
Tin  grey  Tin  white 
13.2o C

 Cubic   Tetragonal 
13.2o C
 KNO3 KNO3
 Rhombohedral   Orthorhombic 
Q: The existence of an element in more than one crystalline form is
called allotropy and these forms of the element are called allotropes
or allotropic forms. Allotropes have:
A) Same physical and chemical properties
B) Same chemical but different physical properties
C) Different physical but same chemical properties
D) Different chemical but same physical properties
Answer Explanation: (B)
Polymorphs have the same chemical but different physical
properties
Elements Crystalline forms
Sulphur, S Rhombic, Monoclinic
Carbon, C Cubic (diamond), hexagonal (graphite)
Tin, Sn Grey tin (cubic), white tin (tetragonal)
MCQ:
Amorphous means ________:
A) Without any specific space
B) Without any transition temperature
C) Without any force
D) Without motion
Answer Explanation: (A)
Amorphous means without any specific space
MCQ: Electrical conductivity of graphite is greater in one direction
than in other due to:
A) Isomorphism C) Anisotropy
B) Cleavage plane D) Symmetry
Answer Explanation: (C)
Electrical conductivity of graphite is greater in one direction than in
other due to anisotropy
 61
4. Types of Crystalline Solids
Classification of solids on the basis of chemical bonding

Properties Metallic solids Ionic solids Covalent solids Molecular solids

1. Structure Covalent solids (2-types)
i. Examples Na, Fe, Cu NaCl, CaO, K2SO4 i. When the covalent I2, S8, C10H8, HCl, CH4
ii. Constituent Atoms Ions show bonds join to form Molecules
particles polymorphism giant molecules e.g.
and isomorphism diamond, SiC, Al N
iii. Type of Metal elements Me t al /non -m etal (network strucutre) No n -metal elements or
substance with low compound ii. When atoms jo in to non -m etal /non -metal
electronegativity (a compound of form the covalent compound (elements with
elements with a bonds and separates high electronegativity)
large difference layers are produced
electronegativity) e.g. graphite, CdI 2,
NbN.
No n -metal element in
group IV or its compound Contd..
 62

Properties Metallic solids Ionic solids Covalent solids Molecular solids

2. Bonding Attraction of outer Attraction of Atoms are linked through St rong covalent bonds
in the solid mobile electrons for positive ions for the whole structure by hold atoms together
positive nuclei negative ions very strong covalent within the separated
binds atoms strong ionic bonds from one atom to molecules, separate
together by strong bonds the next molecules are held
metallic bonds Na +( g ) +Cl -(g ) together by weak van der
→Na+Cl-(s) waal’s bonds
3. Properties No n -volatile high No n -volatile high No n -volatile very high Vo latile low m.pt, low b.pt
i. Volatility m.pt, high b.pt, high m.pt, high b.pt, m.pt, very high b.pt, very low latent heats
latent heats high latent heats high latent heats
St ate at room Usually solid Solid Solid Us ually gases or volatile
temperature liquids

Contt..
 63

Properties Metallic solids Ionic solids Covalent solids Molecular solids

ii. Hardness Hard, yet malleable Hard and brittle Very hard and brittle Soft
malleability Go od conductors when No n -conductors No n -conductors No n -conductors when
iii. Conductivity solid or liquid when solid. Go od (graphite is an solid, liquid and in
iv. Solubility El ectrical conductivity conductors when exception) aqueous solution. A few
of metals decreases molten or in (e.g. HCl) react with water
with the increase of aqueous solution to form electrolytes
temperature electrolytes
Insoluble in polar and So luble in polar Insoluble in polar solvents
non -p olar solvents, but solvents (e.g. Insoluble in all solvents (e.g. H2 O), soluble in non -
soluble in liquid metals H2 O) insoluble in polar solvents (e.g. CCl4)
non -p olar
solvents (e.g.
CCl4)
 64
MCQ
Which of the following statements about ionic solids, covalent solids
and molecular solids is incorrect?

Opt. Properties Ionic solids Covalent solids Molecular solids

A) Example NaCl, CaO Diamond, SiC I2, CO2, HCl, Ice
B) Basic component Ions Atom Molecule
No n-conductor in No n-conductor No n-conductor except
C) Electrical conductivity
solid state except graphite HCl in H2O
Ve ry high M. Ps and Ve ry low M.Ps and
D) M.P and B.P Very high M.Ps and B.Ps
B.Ps B.Ps
ANSWER EXPLANATION: (D)
It is incorrect statement
The correct statement is as follow:
Opt Properties Ionic solids Covalent solids Molecular solids
D) M.P and B.P High M.Ps and B.Ps Very high M.Ps and B.Ps Low M.Ps and B.Ps
 65
Q: Which of the following sets of solid elements A, B and C includes
a giant metallic structure, a macromolecular structure and a simple
molecular structure?
A) Na, Mg, Al C) Al, Si, S
B) C, Si, Sn D) Al, S, Si
ANSWER EXPLANATION: (C)

Elements Type of structure

 Al Metallic structure
 Si Macromolecular structure
S Simple molecular structure
 5. Crystal Lattices
(a) Unit Cell

The smallest part of the crystal lattice which has all the characteristic features
of the entire crystal is called unit cell. It is a representative of the crystal.
Which is true statement for the unit cell:
I. The crystal may be considered to consist of infinite number of unit cells
II. A unit cell is characterized by the distances a, b, c along the three of its
edges, and the angles α, β and 
III.Angles β is between edges c and a, angle  is between a and b and angle α
is between edges b and c.
A) I only C) II and III only
B) II only D) I, II and III
 Answer Explanation (D)
All of the following statements are true related with
unit cell:
 The crystal may be considered to consist of infinite
number of unit cells
 A unit cell is characterized by the distances a, b, c
along the three of its edges, and the angles α, β and .
 Angles β is between edges c and a, angle  is between a
and b and angle α is between edges b and c.
 68

NaCl Crystal
Name Geometry Structure Number of formula per units cell
= 8/8 + 6/2 = 1+3 = 4
• Number of formula per units cell = 4
Face centred • Th ere are eight corners and eight chloride ions 8/8.
Sodium
cubic So per corner 8/8
chloride
structure • 6 Cl - ions are present at the face centres and each is
being shared between two cells 6/2.
• Number of formula units per unit cell 8/8 + 6/2 = 4
 69

MCQ: All of the following statements are correct about NaCl EXCEPT:
A) Independent molecules of NaCl do not exist in the vapour phase
B) Every Na+ ion is surrounded by six Cl- ions and vice versa
C) Number of formula units of NaCl per unit cell is 4
D) Solid NaCl exists in the crystal lattice form
ANSWER EXPLANATION: (A)
It is incorrect statement
The correct statement is as follow:
Independent molecules of NaCl exists in the vapour phase
 MCQS: 70
Which of the following are the types of cubic lattices
(A) Simple cubic lattice (C) Face Centered Cubic lattice
(B) Body centered lattice (D) All of these
Answer Explanation (D)

Types of structure Notation Coordination number Examples

Simple cubic structure Cubic P-type lattice 6 Mn
Body centered cubic structure (bcc) Cubic I-type lattice 8 Na, K, W
Face centered cubic structure (fcc) Cubic F-type lattice 12 Sc, Ti, V
Other structures
Hexagonal close packed structure (hcc) Hcc 12 Mn, Cd, Zn
 (b) Types of Unit Cells 71
Type of unit cell Definition
It is a uni t cell whi ch hav el atti ce poi nts onl y at the
Simple unit cell
corners
It is a uni t cell whi ch hav el atti ce poi nts not onl y at
Face centred unit cell the corners but also at the centred of each faces
It is a uni t cell whi ch hav el atti ce poi nts not onl y at
Body centred unit cell
the corners but also centre of the body

MCQ: A cubic crystal has ____ center of symmetry

A) 1 C) 3
B) 2 D) 6
Answer Explanation: (A)
A cubic crystal has 1 center of symmetry
 72
6. Lattice Energy
MCQ
Lattice energy (∆Holatt) is the amount of heat energy released in the
_______ of one mole of ionic solid from its gaseous ions:
A) Combustion C) Dissociation
B) Formation D) Dissolution
Answer Explanation: (B)
Lattice energy is the amount of heat energy released in the
formation of one mole of ionic solid from its gaseous ions.
e.g (∆Holatt) of NaCl = -787 kJmol-1
73
 74

Solution (A)
Note:
FOR FURTHER MCQs SEE PRACTICE BOOK
WITH DETAILED EXPLANATION
Thank you!