CHP No 4

CHAPTER
4 LIQUIDS AND SOLIDS
Animation 4.1: Solid, Liquid, Gas

Source & Credit: everythingscientiic
4 LIQUIDS AND SOLIDS eLearn.Punjab
INTRODUCTION
The existence of matter in our surrounding in the form of gases, liquids and solids is due to
diference of interacting forces among the constituent particles.
4.1 INTERMOLECULAR FORCES
To understand the properties of liquids and solids, we need to know the kinds of intermolecular
forces present in them and their relative strength. It is important to realize that the attraction
between the molecules is much weaker than the attraction between atoms within a molecule. In a
molecule of HCl, there is a covalent bond between H and Cl which is due to the mutual sharing of
electrons. Both atoms satisfy their outermost shells and it is their irm need to remain together,
hence this linkage is very strong.
HCl molecules in the neighbourhood attract each other, but the forces of attraction are
weak. These forces are believed to exist between all kinds of atoms and molecules when they are
suiciently close to each other. Such intermolecular forces are called van der Waals forces and they
have nothing to do with the valence electrons.
These intermolecular forces bring the molecules close together and give particular physical
properties to the substances in gaseous, liquid and solid states. Four types of such forces are
mentioned here.
1. Dipole-dipole forces
2. Ion-dipole forces
3. Dipole-induced dipole forces
4. Instantaneous dipole-induced dipole forces or London dispersion forces
2
Anim ation 4.2 : Interm olecular forces

Source & Credit: interm olecularforcess
4.1.1 Dipole-dipole Forces
In case of HCl molecule both atoms difer in electronegativity. Chlorine being more
electronegative, develops the partial negative charge and hydrogen develops the partial positive
charge. So, whenever the molecules are close to each other, they tend to line up. The positive end
of one molecule attracts the negative end of the other molecule and these electrostatic forces of
attraction are called dipole-dipole forces. However, thermal energy causes the molecules not to
have a perfect alignment.
3
Anyhow, there is a net attraction between the polar molecules. These forces are called as
dipole-dipole forces and they are approximately one percent as efective as a covalent bond.
The strength of these forces depends upon the electronegativity diference between the bonded
atoms and the distance between the molecules. The distances between molecules in the gaseous
phase are greater so these forces are very
weak in this phase. In liquids these forces
are reasonably strong. The examples of
the molecules which show dipole-dipole
attractions are numerous. Two of these
are given below i.e., for HCl and CHCl3
(chloroform) Fig (4.1).
Greater the strength of these dipole-
dipole forces, greater are the values of
Show Fig. (4.1) Dipole - dipole forces present in HC1
thermodynamic parameters like melting molecules and chloroform (CHCl3) molecules.
points, boiling points, heats of vapourization
and heats of sublimation.
4.1.2 Dipole-induced Dipole Forces
Sometimes, we have a mixture of substances containing polar and non-polar molecules. The
positive end of the polar molecule attracts the mobile electrons of the nearby non-polar molecule.
In this way polarity is induced in non-polar molecule, and both molecules become dipoles. These
forces are called dipole-induced dipole forces or as Debye forces. The following igure makes the
idea clear Fig (4.2).
Fig (4.2) Dipole-induced dipole interactions
4
4.1.3 Instantaneous Dipole-induced Dipole Forces or London Dispersion Forces
Intermolecular forces among the polar molecules, as discussed in section 4.1.1 are very easy to
understand. But the forces of attraction present among the non-polar molecules like helium,
neon, argon, chlorine and methane need special attention because under normal conditions
such molecules don’t have dipoles. We know that helium gas can be liqueied under appropriate
conditions. In other words forces of attraction operate among the atoms of helium which cause
them to cling together in the liquid state.
A German physicist Fritz London in 1930 ofered a simple explanation for these weak attractive
forces between non-polar molecules.
In helium gas, the electrons of one atom inluence the moving electrons of the other atom.
Electrons repel each other and they tend to stay as far apart -as possible. When the electrons of
one atom come close to the electron 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 (4.3). 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.
Fig. (4.3) Instantaneous dipole-induced

dipole attractions between helium atoms.
This instantaneous dipole then disturbs the electronic cloud of the other nearby atom. So,a dipole
is induced in the second atom. This is called induced dipole. The momentary force of attraction
created between instantaneous dipole and the induced dipole is called instantaneous dipole-
induced dipole interaction or London force.
5
It is a very short-lived attraction because the electrons keep moving. This movement of electrons
cause the dipoles to vanish as quickly as they are formed. Anyhow, a moment later, the dipoles will
appear in diferent orientation and again weak attractions are developed.
London forces are present in all types of molecules whether polar or non-polar, but they are very’
signiicant for non-polar molecules like Cl2, H2 and noble gases (helium, neon,etc.)
Anim ation 4.3 : London Dispersion Forces

Source & Credit: dy nam icscience
4.1.4 Factors Affecting the London Forces
London forces are weaker than dipole- dipole interactions. The strength of these forces depend upor
the size of the electronic cloud of the atom or molecules. When the size of the atom or molecule is
large then the dispersion becomes easy and these forces become more prominent. The elements
of the zero group in the periodic table are all mono-atomic gases. They don’t make covalent bonds
with other atoms because their outermost shells are complete. Their boiling points increase down
the group from helium to radon. Boiling points of noble gases are given in Table (4.1)
The atomic number increases down the group and the outermost electrons move away from the
nuclei. The dispersion of the electronic clouds becomes more and more easy. So the polarizability
of these atoms go on increasing.
6
Polarizability is the quantitative Table(4.1) Boiling points of halogens and

measurement of the extent to which noble gases
the electronic cloud can be polarized or
distorted. When we say that a species (atom,
molecule or ion) is polarized, it means
that temporary poles are created. This is
possible if electronic cloud can be disturbed
or distorted. This increased distortion of
electronic cloud creates stronger London
forces and hence the boiling points are
increased down the group.
Similarly, the boiling points of halogens
in group VII-A also increase from luorine to
iodine Table (4.1). All the halogens are non-
polar diatomic molecules, but there is a big
diference in their physical states at room
temperature. Fluorine is a gas and boils at
-188.1 °C, while iodine is a solid at room
temperature which boils at +184.4 °C. The
polarizability of iodine molecule is much
greater than that of luorine.
Another important factor that afects the strength of London forces is the number of atoms
in a non-polar molecule. Greater the number of atoms in a molecule, greater is its polarizability. Let
us discuss the boiling points of saturated hydrocarbons. These hydrocarbons have chain of carbon
atoms linked with hydrogen atoms. Compare the length of the chain for C2H6 and C6H14.
They have the boiling points - 88.6 °C and 68.7 C,respectively. This means that the molecule with
a large chain length experiences stronger attractive forces. The reason is that longer molecules have
more places along its length where they can be attracted to other molecules. It is very interesting to
know that with the increasing molecular mass of these hydrocarbons, they change from gaseous to
liquid and then inally become solids. The Table (4.2) gives the boiling points and the physical states
of some hydrocarbons.
7
Table (4.2) Boiling points and physical states of some hydrocarbons

Name B.P Physical state Name B.P Physical state
0
C (1 atm) at S.T.P 0
C (1 atm) at S.T.P
Mathane -164 Gas Pentane 36.1 Liquid
Ethane -88.6 Gas Hexane 68.7 Liquid
Propane -42.1 Gas Decane 174.1 Liquid
Butane 0.5 Gas Isodecane 327 Solid
4.1.5 Hydrogen Bonding
To understand hydrogen bonding, let us consider the molecule of water. Oxygen is more
electronegative element as compared to hydrogen, so water is a polar molecule. Hence there will
be dipole-dipole interactions between
partial positively charged hydrogen atoms
and partial negatively charged oxygen
atoms. Actually, hydrogen bonding is
something more than simple dipole-
dipole interaction. Firstly, oxygen atom
has two lone pairs. Secondly hydrogen
has suicient partial positive charge. Both
the hydrogen atoms of water molecule
create strong electrical ield due to their
small sizes.
The oxygen atom of the other molecule
links to form a coordinate covalent bond
with hydrogen using one of its lone pairs
of electrons. Fig (4.4).
Thus loose bond formed is deinitely Fig (4.4) Hydrogen bonding in water.
stronger than simple dipole-dipole

interaction. Because of the small size of the hydrogen atom, it can take part in this type of bonding.
This bonding acts as a bridge between two electronegative oxygen atoms. Hence hydrogen bonding
is the electrostatic force of a atraction between a highly electronegative atom and partial positively
charged hydorgen atom.
8
The electronegative atoms responsible for creating hydrogen bonding are luorine, oxygen,
nitrogen and rarely chlorine. The strength of hydrogen bond is generally twenty times less than
that of a covalent bond.
Anim ation 4.4 : hy drogen bonding

Source & Credit: stream 1
It is not advisable to limit the hydrogen bonding to the above-m entioned electronegative atoms.
The three chlorine atoms in chloroform are responsible for H- bonding with other molecules.
These atoms deprive the carbon atom
of its electrons and the partial positively
charged hydrogen can form a strong
hydrogen bond with oxygen atom of
acetone Fig (4.5).
Fig (4.5) Hydrogen bonding between

chloroform and acetone
9
The hydrogen bonding present in the

molecules of ammonia and those of
hydrolouric acid can be depicted as follows
Fig (4.6).The molecules of HF join with each
other in a zig- zag manner.
The exceptional, low acidic strength of
HF molecule as compared to HCl, HBr and
HI is due to this strong hydrogen bonding,
because the partial positively charged
hydrogen is entrapped between two highly
electronegative atoms.
Fig (4.6) Hydrogen bonding in
NH3 and HF molecules.
4.1.6 Properties and Application of Compounds Containing Hydrogen Bonding
1. Thermodynamic Properties of Covalent Hydrides
Our discussion shows that hydrogen bonding exists in compounds having partial positively charged
hydrogen and highly electronegative atoms bearing partial negative charge. Obviously such
intermolecular attractions will inluence the physical properties like melting and boiling points. Let
us compare the physical properties of hydrides of group IV-A, V-A, VI-A and VII-A. The graphs are
plotted between the period number of the periodic table on x-axis and boiling points in kelvin on
y-axis Fig (4.7).
10
Fig (4.7) A Graph between period number and the boiling points of hydrides of IV-A, V-A, VI-A
and VII-A group elements.
A look at the boiling points of hydrides of group IV-A convinces us, that they have low boiling
points as compared to those of group V-A, VI-A, VII-A. The reason is that these elements are
least electronegative. CH4 has the lowest boiling point because it is a very small molecule and its
polarizability is the least.
When we consider the hydrides of group V-A, VI-A, VII-A then NH3, H20 and HF show maximum
boiling points in the respective series. The reason is, the enhancec electronegative character of N,
0 and F. That is why, water is liquid at room temperature, but H2S and H2Se are gases.
It is interesting to know that the boiling point of water seems to be more afected by hydrogen
bonding than that of HF Fluorine is more electronegative than oxygen. So, we should expect
H-bonding in HF to be stronger than that in water and as a result the boiling point of HF should be
higher than that of H20. However, it is lower and the reason is that the luorine atom can make only
one hydrogen bond with electropositive hydrogen of a neighboring molecule. Water can form two
hydrogen bonds per molecule, as it has two hydrogen atoms and two lone pairs on oxygen atom.
Ammonia can form only one hydrogen bond per molecule as it has only one lone pair.
11
The boiling point of HBris slightly higher than that of HCl. It means that chlorine is
electronegative enough to form a hydrogen bond. Sometimes it is thought that HCl has a strong
dipole-dipole interaction but in reality, it is a border line case. The hydrides of fourth period GeH4,
AsH3, H2Se, HBr show greater boiling points than those of third period due to greater size and
enhanced poiarizabilities.
2. Solubility of Hydrogen- Bonded Molecules
Water is the best example of H-bonded system. Similarly 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. Similarly carboxylic acids are also soluble in water, if their sizes
are small. 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.
3. 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. When the temperature of water
is decreased and ice is formed then the molecules
become more regular and this regularity extends
throughout the whole structure. Empty spaces
are created in the structure as shown in the
following Fig (4.8b). That is why when water
freezes it occupies 9% more space and its density
decreases. The result is that ice loats on water.
The structure of ice is just like that of a diamond
because each atom of carbon in diamond is at
the center of tetrahedron just like the oxygen of
water molecule in ice, Fig (4.8 b).
Fig (4.8 a) Structure of liquid water
12
The lower density of ice than liquid water at 0

°C causes water in ponds and lakes to freeze from
surface to the downward direction. Water attains
the temperature of 4°C by the fall of temperature
in the surrounding. As the outer atmosphere
becomes further cold, the water at the surface
becomes less dense. This less dense water below
4 °C stays on the top of slightly warm water
underneath. A stage reaches when it freezes. This
layer of ice insulates the water underneath for
further heat loss. Fish and plants survive under
this blanket of ice for months. Fig (4.8 b) Structure of ice
Keeping the whole discussion in view we are
forced to believe that the pattern of life for the plants and animals would have been totally diferent
in the absence of hydrogen bonding in water.
4. Cleansing Action of Soaps and Detergents
Soaps and detergents perform the cleansing action because the polar part of their molecules
are water soluble due to hydrogen-bonding and the non-polar parts remain outside water, because
they are alkyl or benzyl portions and are insoluble in water.
5. Hydrogen Bonding in Biological Compounds and Food Materials
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 into a spiral. This spiral is called a helix. Such
a helix may either be right handed or left handed. In the case of right handed helix the groups like
>N H 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-ray analysis has shown that on the average
there are 27 amino acid units for each turn of the helix, Fig (4.9 a).
Deoxyribonucleic acid (DNA) has two spiral chains. These are coiled about each other on a
common axis. In this way, they give a double helix. This is 18-20 Å in diameter. They are linked
together by H-bonding between their sub units, Fig (4.9 b).
13
Fig (4.9 a) Hydrogen bonding
Fig (4.9 b) Hydrogen bonding in

DNA double helix
The food materials like carbohydrates include glucose, fructose and sucrose. They all have
-OH groups in them which are responsible for hydrogen bonding in them.
6. Hydrogen Bonding in Paints, Dyes and Textile Materials
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.
We use cotton, silk or synthetic ibres for clothing. Hydrogen bonding is of vital importance
in these thread making materials. This hydrogen bonding is responsible for their rigidity and the
tensile strength.
14
4.2.0 EVAPORATION
In order to understand evaporation, we have to examine the movement of molecules in liquids.

The molecules of a liquid are not motionless. The energy of molecules is not equally distributed.
The molecules which have low kinetic energy move slowly, while others with high kinetic energy
move faster. If one of the high speed molecules reaches the surface, it may escape the attractions
of its neighbouring molecules and leaves the bulk of the liquid. This spontaneous change of a
liquid into its vapours is called evaporation and it continues at all temperatures.
Evaporation causes cooling. The reason is that when high energy molecules leave the liquid and
low energy molecules are left behind, the temperature of the liquid falls and heat moves from the
surrounding to the liquid and then the temperature of the surrounding also falls.
Anim ation 4.5 : Evaporation

Source & Credit: stem
15
There are many factors which control the rate of evaporation of a liquid. Since evaporation occurs
from liquid surface, so if surface area is increased then more molecules are able to escape and
liquid evaporates more quickly. For liquids having same surface area, the rate of evaporation is
controlled by the temperature and the strength of intermolecular forces.
At high temperature, the molecules having greater energy increase and so rate of evaporation
increases. Similarly, if intermolecular forces are weak, the rate of evaporation is faster. For example,
gasoline, whose molecules experience weaker London forces of attraction, evaporate much faster
than water.
4.2.1 Vapour Pressure
When the molecules of a liquid leave the open surface, they are mixed up with air above the
liquid. If the vessel is open these molecules go on leaving the surface. But if we close the system
the molecules of liquid start gathering above the surface. These molecules not only collide with the
walls of the container, but also with the surface of the liquid as well.
There are chances that these molecules are recaptured by the surface of liquid. This process is
called condensation. The two-processes i.e., evaporation and condensation continue till a stage
reaches when the rate of evaporation becomes equal to the rate of condensation. This is called the
state of dynamic equilibrium Fig (4.10). So the vapour pressure of a liquid is a pressure exerted by
the vapours of the liquid in equilibrium with the liquid at a given temperature.
Liquid ฀฀ ฀฀
฀฀ Vapour
Fig (4.10) Evaporation of a liquid and establishment

of dynamic equilibrium between liquid and its vapours.
16
The number of molecules leaving the surface is just equal

to the number of molecules coming back into it at a constant
temperature. The molecules which are in the liquid state at any
moment may be in vapour state in the next moment.
The magnitude of vapour pressure does not depend upon the
amount of liquid in the container or the volume of container. It also
does not depend on surface area of a liquid. The larger surface area
Anim ation 4.6 : Vapour Pressure
also presents a larger target for returning the molecules, so the Source & Credit: mecalux
rate of condensation also increases.
Vapour Pressure Increases with Temperature
The values of vapour pressures of various liquids depend fairly upon the nature of
liquids i.e. on the sizes of molecules and intermolecular forces, but the most important parameter
which controls the vapour pressure of a liquid is its temperature. At an elevated temperature, the
kinetic energy of molecules is enhanced and capability to leave the surface increases.
It causes the increase of vapour pressure. Table(4.3) Tablc (4.3) Vapour pressures of water
shows change in vapour pressure of water at diferent (torr) at various temperatures
temperatures. The Table (4.3) shows that increases
of vapour pressure goes on increasing for the same Temperature Vapour
diference of temperature from 0°C to 100°C for water. There is (0C) Pressure
increase of vapour pressure from 4.579 torr to 9.209 torr for change (Torr)
of temperature from 0°C to 10°C. But the increase is from 527.8 torr 0 4.579
to 760 torr when temperature changes from 90°C to 100°C. 10 9.209
The diference in the strength of intermolecular forces in diferent 20 17.54
liquids is directly related to their vapour pressures at a particular 30 31.82
temperature. The stronger the intermolecular forces the lower 37 47.07
the vapour pressure. The following Table (4.4) shows that at 20 °C 40 55.32
isopentane has the highest vapour pressure, while glycerol has the 50 92.51
lowest. 60 149.4
70 233.7
80 355.1
90 527.8
100 760.0
17
4.2.2 Measuremerr of Vapour Pressure
There are many methods for the measurement of vapour pressure of a liquid. One of
the important methods is described in the following paragraph.
Table (4.4) Vapour pressure of some

important liquids at 20°C
Name of compound Vapour pressure
at 20 0C (torr)
Isopentane 580
Ethyl ether 442.2
Chloroform 170
CarbonTetrachloride 87
Ethanol 43.9
Mercury 0.012
Glycerol 0.00016
Manometric Method
Manometric method is comparatively an accurate method. The liquid whose vapour pressure is
to be determined is taken in a lask placed in a thermostat, as shown in the Fig(4.11). One end
of the tube from the lask is connected
to a manometer and the other end
is connected to a vacuum pump. The
liquid is frozen with the help of a
freezing mixture and the space above
the liquid is evacuated. In this way, the
air is removed from the surface of the
liquid alongwith the vapours of that
liquid. The frozen liquid is then melted
to release any entrapped air. Liquid is
again frozen and realeased air To is
evacuated. This process is repeated Fig. (4.11) Measurement of vapour pressure of a
in the heights of the columns of-Hg in liquid by manometric method
many times till almost all the air is
removed.
18
Now the liquid is warmed in the thermostat to that temperature at which its vapour pressure in
the lask is to be determined. Diference in the heights of the columns of-Hg in liquid by manometric
method the two limbs of the manometer determines the vapour pressure of the liquid.
The column of mercury in the manometer facing the vapours of the liquid is depressed. The
other column, which faces the atmospheric pressure, rises. Actually, the pressure on the surface of
the liquid in the lask is equal to the sum of the atmospheric pressure and the vapour pressure of
liquid. For this reason, the column of manometer facing the liquid is more depressed than facing
the atmosphere, and it is given by the following equation.
P = Pa + ∆h
Where P = Vapour pressure of the liquid at one atm pressure.
P= Atmospheric pressure.
∆h = Diference in the heights of the mercury levels in the two limbs
of the manometer, giving us the vapour pressure of liquid.
4.2.3 Boiling Point
When a liquid is heated, the vapour pressure goes on increasing. A stage reaches when
the vapour pressure of the liquid becomes equal to the external atmospheric pressure. This
temperature is called the boiling point of the liquid.
The reason for this is that the bubbles of vapours
which are formed in the interior of the liquid have
greater internal pressure than atmospheric pressure
on the surface of liquid. This thing makes the bubble
to come out of the liquid and burst upon the surface.
Thus a constant stream of bubbles comes out at the
boiling point.
When a liquid is heated, the kinetic energy of
its molecules increases and hence the temperature
also increases. At the boiling point, the kinetic energy
of the molecules becomes maximum and any further
heating at this stage will not increase the temperature.
Anim ation 4.7 : Boiling Point
Source & Credit: chem
19
This heat will only be utilized to break the intermolecular forces and convert the liquid into its
vapours. The amount of heat required to vapourize one mole of a liquid at its boiling point is
called its molar heat of vapourization. The molar heat of vapourization of water is 40.6 kjmol-1.
The boiling points of some commonly available liquids at one atmospheric pressure are shown in
the Table (4.5).
Table (4.5) Boiling points of some

common liquids at 760 torr.
Liquid B.P (0C) Liquids B.P (0C)
Acetic Acid 118.50 Carbon tetrachloride 76.50
Acetone 56.00 Ethanol 78.26
Aniline 184.4 Naphthalene 218.00
Benzene 80.15 Phenol 181.80
Carbon disulphide 46.30 Water 100.00
The Fig. (4.12) shows the variation of vapour pressure of water, ethyl alcohol, ethylene glycol
and diethylether with temperature. It shows that the liquids reach upto their boiling points when their
vapour pressures are equal to 760 torr at
sea level. The way these curves start at 0
0
C is interesting. Water takes start at 4.8
torr while diethyl ether at around 200 torr.
This is due to diference in the strengths
of their intermolecular forces. The curve
for water goes alongwith temperature
axis to a greater extent at the beginning
as compared to ether. It means that water
can hardly overcome its intermolecular
forces at low temperatures. It is clear
from the curves that the vapour pressure
increases very rapidly when the liquids
are closer to their boiling points.
Fig (4.12) Vapour pressures(torr) of four common liquids shown as a

function of temperature(°C).
20
4.2.4 Boiling Point and External Pressure
We have already explained that when vapour pressure of a liquid becomes equal to the
external pressure then the liquid boils, so when external pressure is changed, its boiling point
will also be changed. A liquid can be made to boil at any temperature by changing the external
pressure. When the external pressure is high the liquid requires greater amount of heat to equalize
its vapour pressure to external pressure. In this way boiling point is raised. Similarly, at a lower
external pressure a liquid absorbs less amount of heat and it boils at a lower temperature.
For example, water shows B.P of 120 °C at 1489 torr pressure and boils at 25 °C at 23.7 torr.
Water boils at 98 °C at Murree hills due to external pressure of 700 torr while at the top of Mount
Everest water boils at only 69 0C 323 torr.
We can increase the external pressure artiicially on the surface of boiling water by using a
pressure cooker. Pressure cooker is a closed container. The vapours of water formed are not allowed
to escape. In this way, they develop more pressure in the cooker and the boiling temperature
increases. As more heat is absorbed in water, so food is cooked quickly under increased pressure.
Liquids can be made to boil at low temperatures, where they can be distilled easily. This process
is called vacuum distillation. Vacuum distillation has many advantages. It decreases the time for
the distillation process and is economical because less fuel is required. The decomposition of many
compounds can be avoided e.g. glycerin boils at 290 °C at 760 torr pressure but decomposes at this
temperature. Hence, glycerin cannot be distilled at 290 °C. Under vacuum, the boiling temperature
of glycerin decreases to210 0C at 50 torr. It is distilled at this temperature without decomposition
and hence can be puriied easily.
4.2.5 Energetics of Phase Changes
Whenever, matter undergoes a physical change, it is always accompanied by an energy

change. This change in energy is the quantitative measurement of the diference in the strength of
intermolecular forces.
The change in energy is mostly in the form of heat. If a physical or a chemical change
takes place at a constant pressure, then the heat change during this process is also called
enthalpy change. This is denoted by ΔH. These enthalpy changes are usually expressed per mole
of the substances. Three types of enthalpy changes are associated with usual physical changes.
21
(i) Molar Heat of Fusion (ΔHf)
It is the amount of heat absorbed by one mole of a solid when it melts into liquid form at its
melting point. The pressure, during the change is kept one atmosphere.
(ii) Molar Heat of Vapourization (ΔHv)
It is the amount of heat absorbed when one mole of a liquid is changed into vapours at its
boiling point. The pressure, during the change is kept one atmosphere.
(iii) Molar Heat of Sublimation (ΔHs)
It is the amount of heat absorbed when one mole of a solid sublimes to give one mole of
vapours at a particular temperature and one atmospheric pressure.
All these enthalpy changes are positive, because they are endothermic processes.
4.2.6 Energy Changes and Intermolecular Attractions
When a solid substance melts then atoms, molecules or ions undergo relatively small changes
in intermolecular distances and the potential energy also undergoes a small change. But when a
liquid evaporates, then larger changes in intermolecular distances and in potential energy takes
place. So ΔH of vapourization of a substance is greater than ΔH of fusion. The values of ΔHs are even
larger than ΔHv because attractive forces in solids are stronger than those in liquids.
The values of ∆Hv and ∆Hs tell us directly the energy needed to separate molecules from each
other. So from these values, we can compare the strengths of intermolecular forces in diferent
compounds.
From the following Table (4.6), we are convinced that ΔHv for H20, NH3 and S02 are reasonably
high due to polar nature of molecules. ΔHV for iodine is the highest amongst its family members
due to its greater polarizability. Similarly, hexane (C6H14) has the highest ΔHv value amongst the
hydrocarbons due to larger size of its molecules. Actually, the London dispersion forces in I2 and
C6H14 are suiciently strong and these are responsible for such a behaviour.
22
Table (4.6) Heats of

Vaporization
of some substances
Substance ΔHv (kJ/mol)
H2O +40.6
NH3 +21.7
HCl +15.6
SO2 +24.3
F2 +5.9
Cl2 +10.00
Br2 +15.00
I2 +22.00
CH4 +8.60
C2H6 +15.1
C3H8 +16.9
C6H14 30.1
4.2.7 Change of State and Dynamic Equilibrium
Whenever, a change of state occurs the system moves towards the condition of dynamic
equilibrium. Dynamic equilibrium is a situation when two opposing changes occur at equal rates.
Being a chemist, we should know that the concept of dynamic equilibrium is the fate or the ultimate
goal of all the reversible chemical reactions and all the physical changes.
At 0°C, solid water (ice) exists in dynamic equilibrium with liquid water.
0o C
ice ฀฀ ฀฀ ฀฀฀฀ water
4.3 Liquid Crystals
Whenever we study the properties of crystalline solids, we come to know that the pure solids
melt sharply. The temperature remains constant at the melting point until all the solid melts.
23
In 1888, Frederick Reinitzer, an Austrian botanist discovered a universal property. He was

studying an organic compound cholesteryl benzoate. This compound turns milky liquid at 145°C
and becomes a clear liquid at 179°C. When the substance is cooled, the reverse process occurs.
This turbid liquid phase was called liquid crystal.
Uptil now, it has been reported that, there are many crystalline solids which melt to a turbid
liquid phase, before inally melting to a clear liquid. These turbid liquid phases can low as liquids.
They have the properties like liquids as surface tension, viscosity, etc. But it is very interesting to
know that the molecules of such turbid liquids possess some degree of order as well. It means that
these turbid liquids resemble crystals in certain properties and the most important properties are
optical ones. These turbid liquids are hence called liquid crystals. So, a liquid crystalline state
exists between two temperatures i.e. melting temperature and clearing temperature. A
crystalline solid may be isotropic or anisotropic, but liquid crystals are always anistropic.
Crystal ฀฀ ฀฀
฀฀ Liquidcrystal ฀฀ ฀฀
฀฀ Liquid
From 1888 to until about 30 years ago, liquid crystals were largely a laboratory curiosity. But
now they have found a large number of applications.
Those substances which make the liquid crystals are often composed of long rod like molecules.
In the normal liquid phase, these molecules are oriented in random directions. In liquid crystalline
phase, they develop some ordering of molecules. Depending upon the nature of ordering, liquid
crystals can be divided into nematic, smectic and cholesteric.
The properties of liquid crystals are intermediate between those of crystals and isotropic
liquids. They have the luidity of the liquids and the optical properties of the crystals.
Uses of Liquid Crystals
Due to the remarkable optical and electrical properties, liquid crystals ind many practical
applications. Many organic compounds and biological tissues behave as liquid crystals. The unique
properties of liquid crystals have intrigued the scientists since their discovery, nearly hundred years
ago. Some of their important uses are as follows.
(i) Like solid crystals, liquid crystals can difract light. When one of the wavelengths of white
light is relected, from a liquid crystal it appears coloured. As the temperature changes, the distances
between the layers of the molecules of liquid crystals change. Therefore, the colour of the relected
light changes accordingly. Thus liquid crystals can he used as temperature sensors.
24
(ii) Liquid crystals are used to ind the point of potential failure in electrical circuits. Room
thermometers also contain liquid crystals with a suitable temperature range. As the temperature
changes, igures show up in diferent colours.
(iii) Liquid crystalline substances are used to locate the veins, arteries, infections and tumors.
The reason is that these parts of the body are warmer than the surrounding tissues. Specialists can
use the techniques of skin thermography to detect blockages in veins and arteries. When a layer
of liquid crystal is painted on the surface of the breast, a tumor shows up as a hot area which is
coloured blue. This technique has been successful in the early diagnosis of breast cancer.
(iv) Liquid crystals are used in the display of electrical devices such as digital watches, calculators
and laptop computers. These devices operate due to the fact that temperature, pressure and
electro-magnetic ields easily afect the weak bonds, which hold molecules together in liquid
crystals.
(v) In chromatographic separations, liquid crystals are used as solvents.
(vi) Oscillographic and TV displays also use liquid crystal screens.
25
SOLIDS
4 .4 INTRODUCTION
Solids are those substances which are rigid, hard, have deinite shape and deinite
volume. The atoms, ions and molecules that make up a solid are closely packed. They are held
together by strong cohesive forces. The constituent atoms, ions or molecules of solids cannot move
at random. There exists a well ordered arrangement in solids.
4.4.1 Types of Solids
Solids can be classiied on the basis of the regular arrangements of constituent atoms, ions
or molecules. There are two types of solids in this respect.
(i) Crystalline Solids
Those solids in which atoms, ions or molecules are arranged in a deinite three dimensional
pattern are called crystalline solids This recurring regular geometrical pattern of structure extends
three dimensionally.
(ii) Amorphous Solids
All solids are not crystalline .The word amorphous means shapeless. Amorphous substances
are those whose constituent atoms, ions, or molecules do not possess a regular orderly
arrangement. The best examples are glass, plastics, rubber, glue, etc. These substances have solid
state properties and virtually complete maintenance of shape and volume. But they do not have an
ordered crystalline state.
Many crystalline solids can be changed into amorphous solids by melting them and then
cooling the molten mass rapidly. In this way the constituent particles do not ind time to arrange
them selves.
26
A long range regularity does not exist in amorphous solids but they can possess small regions
of orderly arrangements. These crystalline parts of otherwise amorphous solids are known as
crystallites. Amorphous solids don’t have sharp melting points that is why particles of glass soften
over a temperature range and can be moulded and blown into various shapes. They do not possess
deinite heats of fusion.
4.4.2 Properties of Crystalline Solids
1. Geometrical Shape
All the crystalline solids have a deinite, distinctive geometrical shape due to deinite 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
ine powder.
2. Melting Points
Crystalline solids have sharp melting points and can be identiied from their deinite melting
points.
3. Cleavage Planes
Whenever the crystalline solids are broken they do so along deinite planes. These planes
are called the cleavage planes and 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
Some of the crystals show variation in physical properties depending upon the
direction. Such properties are called anisotropic properties and the phenomenon is referred
to as anisotropy. The physical properties of crystalline solids like refractive index, coeicient of
thermal expansion, electrical and thermal conductivities are sometimes anisotropic in nature for
some crystals.
27
The variation in these properties with direction is due to fact that the orderly arrangement of the
particles in crystalline solids is diferent in diferent directions. For example, electrical conductivity
of graphite is greater in one direction than in another. Actually electrons in graphite are mobile
for electrical conduction parallel to the layers only. Therefore, its conductivity in this direction
is far better than perpendicular to the other direction. Similarly, cleavage itself is an anisotropic
behaviour.
5. Symmetry
The repetition of faces, angles or edges when a crystal is rotated by 360° along its axis is
called symmetry. This an important property of the crystal and there are various types of symmetry
elements found in crystals like, center of symmetry, plane of symmetry and axis of symmetry, etc.
6. Habit of a Crystal
The shape of a crystal in which it usually grows is called habit of a crystal. Crystals are
usually obtained by cooling the saturated solution or by slow cooling of the liquid substance. These
are formed by growing in various directions. If the conditions for growing a crystal are maintained,
then the shape of the crystal always remains the same. If the conditions are changed the shape of
the crystal may change. For example, a cubic crystal of NaCl becomes needle like when 10% urea is
present in its solution as an impurity.
7. Isomorphism
Isomorphism is the phenomenon in which two diferent substances exist in the same
crystalline form. These diferent substances are called isomorphs of each other.
A crystalline form is independent of the chemical nature of the atoms and depends only on
the number of atoms and their way of combinations.
Mostly the ratio of atoms in various compounds are such that isomophism is possible.
Their physical and chemical properties are quite diferent from each other. Anyway, isomorphic
substances crystallize together in all proportions in homogeneous mixtures. Following examples
tell us the nature of the compound, their crystalline forms and the ratio of their atoms.
28
Isomorphs Crystalline form Atomic ratio

NaNO3, KNO3 rhombohedral 1:1:3
K2SO4, K2CrO4 orthorhombic 2:1:4
ZnSO4, NiSO4 -do- 1:1:4
NaF, MgO cubic 1:1
Cu, Ag cubic 1:1
Zn, Cd hexagonal 1:1
The structures of the negatively charged ions like NO3-1 and CO32-, are the same. Similarly shapes of
SO42- and CrO42- are also alike. CO32- and NO31- are triangular planar units, while SO42- and CrO42- are
both tetrahedral.
8. Polymorphism
Polymorphism is a phenomenon in which a compound exists in more than one

crystalline forms. That compound which exists in more than one crystalline forms is tailed a
polymorphic, and these forms are called polymorphs, and these forms are called polymorphs
of each other.
Polymorphs have same chemical properties, but they difer in the physical properties. The diference
in physical properties is due to diferent structural arrangement of their particles.
The following compounds are important polymorphs.
Substance crystalline forms

AgNO3 Rhombohedral, Othorhombic
CaCO3 Trigonal and orthorhombic
9. Allotropy
The existence of an element in more than one crystalline forms is known as allotropy
and these forms of the element are called allotropes or allotropic forms. Sulphur, phosphorus,
carbon and tin are some important examples of elements which show allotropy.
Element Crystalline forms

Sulphur, S Rhombic, monoclinic
Carbon, C cubic (diamond), hexagonal (graphite)
Tin, Sn grey tin (cubic), white tin (tetragonal)
29
10. Transition Temperature
It is that temperature at which two crystalline forms of the same substance can co-ex-
ist in equilibrium with each other. At this temperature, one crystalline form of a substance
changes to another.
Above and below this temperature, only one form exists. A few examples for those substances
which show allotropy and possess a transition temperature are given below
o
13.2 C
(i) Grey Tin (cubic) ฀฀ ฀฀ ฀฀ ฀฀฀฀ White tin (Tetragonal)
o
95.5 C
(ii) Sulphur S8 (rhombic) ฀ Sulphur S8(monoclinic)
฀฀ ฀฀ ฀฀ ฀฀฀
o
128 C
(iii) KNO3 (orthorhombic) ฀฀ ฀฀ ฀฀ ฀฀฀฀ KNO3(rhombohedral)
32.38o C
(iv) Na2S04-10H20 (hydrated form) ฀ ฀ ฀฀ ฀฀฀฀ N a2S04(anhydrous from) + 10 H20
฀ ฀
o
(v) Na2CO3- 10 H20 (higher hydrated form) ฀฀ ฀฀ ฀฀ ฀฀฀฀ Na2CO3-7H20(lowerhydratedform)+3H20
32.38 C
It has been noticed that the transition temperature of the allotropic forms of an element is
always less than its melting point.
4.5 CRYSTAL LATTICE
A crystal is made up of atoms, ions or molecules. In crystalline solids, these atoms, ions or
molecules are located at deinite positions in space.
These positions are represented by points in a crystal.
These points are called as lattice points or lattice sites.
This arrangement of points in a crystal is called crystal
lattice or space lattice.
So a crystal lattice is an array of points representing
atoms, ions or molecules of a crystal, arranged at
diferent sites in three dimensional space. Fig. (4.13)
shows a crystal lattice with a cubic structure.
Fig (4.13) Cubic crystal lattice
30
4.5.1 Unit Cell
When we look at the cubic crystal lattice in Fig (4.14), we see that it is actually composed of
many small parts. The smallest part of the crystal lattice has all the characteristic features of
the entire crystal and is called a unit cell.
It means that a unit cell of a crystal lattice is the smallest block or geometrical igure, from which the
entire crystal can be built up by repeating it in three dimensions. It shows the structural properties
of a given crystal. The complete information about the crystalline structure is present within a unit
cell which repeats itself in three dimensions to form a crystal.
If we know the exact arrangement of atoms in a unit cell, we in fact know their arrangement
in the whole crystal.
The quantitative aspects of a crystal lattice are deduced from the size and shape of the unit cell.
There are three unit cell lengths a, b, c and three unit cell angles a , b and γ. These six parameters
are shown in Fig (4.14)
The angle ‘a’ is between the lengths ‘b’ and ‘c’, the angle ‘b’ is between the sides ‘a’ and ‘c’ and
angle’ γ’ is between sides ‘a’ and ‘b’. The unit cell lengths a, b, c, may be assigned along x, y and z
axis, respectivly but angles a , b and γ have to be decided accordingly. The choice of x, y, z may be
along any of the three axis. These six parameters of the unit cell are called unit cell dimensions or
crystallographic elements.
Keeping in view the structure of the unit cell we can understand the crystal system.
Fig (4.14) Six crystallographic elements specify the size and

shape of a unit cell
31
Anim ation 4.8: Unit Cell

Source & Credit: Com m ons
4.6 CRYSTALS AND THEIR CLASSIFICATION
A crystal system may be identiied by the dimensions of its unit cell along its three edges or axes, a,
b, c and three angles between the axes a , b , γ.
There are seven crystal systems. These seven crystal
systems are described as follows Fig (4.15).
1. Cubic system
In this system all the three axes are of equal length and
all are at right angles to one another.
Animation 4.9: Classiication of Crystals

Source & Credit: w ikipedia
32
2. Tetragonal system
In this system two axes are of equal length and the

third axis is either shorter or larger than the other two. All
angles are 90°.
3. Orthorhombic Or Rhombic System

All the three axes are of unequal length and all are at
right angle to each other.
4. Monoclinic System
All the three axes are of unequal length; two of these
axes are at right angle to each other while the third angle
is greater then 90°.
5. Hexagonal System
In this system two axes are of equal length and are

in one plane making an angle of 120o with each other. The
third axis which is diferent in length than the other two is
at right angle to these two axes.
6. Rhombohedral System Or Trigonal System
All the three axes are of an equal length like cubic

system but the three angles are not equal and lie between Fig (4.15) Seven crystal systems
900 and 120°.
7. Triclinic System
All the three axes and the three angles are unequal and none of the angles is 900.
Table (4.7) shows the unit cell dimensions of the seven crystal systems alongwith their
examples
33
Table (4.7) Seven Crystal Systems
Sr. Crystal system Axes Angles Examples

No
1. cubic a= b= c a= b= γ= 90o
Fe, Cu, Ag, Au, NaCl, NaBr, Dimond
2. Tetragonal a= b ≠ c a= b= γ= 90o
Sn, SnO2, MnO2, NH4Br
3. Orthorhombic a≠b≠c a= b= γ= 90o

Idoine, Rhombic, Sulphur, BaSO4, K2SO4
4. Monoclinic a≠b≠c a= γ= 90o , b ≠ 90o

Sugar, Sulphur, Borax, NaSO.10H2O
5. Hexagonal a= b ≠ c á=â=90o , ã=1200

Graphite, ZnO, CdS, Ice, Zn, Cd
Rhombohedral a= b= c
> a
= =b <γ 90o and 120o
6. Bi, Al2O3, NaNO3, KNO3
or Trignol
7. Triclinic a ≠ b ≠ c a ≠ b ≠ γ ≠ 90o H3BO3, K2Cr2O7, CuSO4.5H2O
4.7 CLASSIFICATION OF SOLIDS
In the preceding section, we noted that the crystals are classiied into seven systems depending
upon the dimensions of the unit cells. A unit cell contains a deinite number of atoms, ions, or
molecules. These atoms, ions or molecules are held together by diferent types of cohesive forces.
These forces may be chemical bonds or some type of interactions. There are four types of crystalline
solids depending upon the type of bonds present in them.
(i) Ionic solids
(ii) Covalent solids
(iii) Metallic solids
(iv) Molecular solids
4.7.1 Ionic Solids
Crystalline solids in which the particles forming the crystal are positively and negatively
charged ions are called ionic solids. These ions are held together by strong electrostatic forces of
attraction. These attractive forces are also called ionic bonds. The crystals of NaCl, KBr, etc are ionic
solids.
34
Properties of Ionic Solids
The cations and anions are arranged in a well deined geometrical pattern, so they are
crystalline solids at room temperature. Under ordinary conditions of temperature and pressure
they never exist in the form of liquids or gases.
Ionic crystals are very stable compounds. Very high energy is required to separate the cations
and anions from each other against the forces of attraction. That is why ionic crystals are very hard,
have low volatility and high melting and boiling points.
Ionic solids do not exist as individual neutral independent molecules. Their cations and anions
attract each other and these forces are non-directional. The close packing of the ions enables
them to occupy minimum space. A crystal lattice is developed when the ions arrange themselves
systematically in an alternate manner.
The structure of the ionic crystals depends upon the radius ratio of cations and anions. For
example.NaCl and CsF have the same geometry because the radius ratio in both the cases is the
same.
In the case of ionic crystals we always talk about the formula mass of these substances and
not the molecular mass, because they do not exist in the form of molecules.
Fig (4.16) Explanation of brittleness of ionic crystals
35
Anim ation 4.10 : Ionic Solids

Source & Credit: Grandinetti
Ionic crystals do not conduct electricity in the solid state, because on account of electrostatic force
existing between them the cations and anions remain tightly held together and hence occupy ixed
positions. Ionic crystals conduct electricity when they are in solution or in the molten state. In both
cases ions become free.
Ionic crystals are highly brittle because ionic solids are composed of parallel layers which
contain cations and anions in alternate positions, so that the opposite ions in the various parallel
layers lie over each other.
When an external force is applied, one layer of the ions slides a bit over the other layer along a plane.
In this way the like ions come in front of each other and hence begin to repel. So, the application
of a little external force develops repulsion between two layers causing brittleness Fig (4.16).
Ionic solids are mostly of high density due to close packing of ions. Such compounds having
the ionic crystals give ionic reactions in polar solvents and these are very fast reactions.
The properties like isomorphism and polymorphism are also associated with the ionic crystals.
In order to understand the structure of ionic crystals, let us explain the structure of sodium chloride
crystals.
36
Animation 4.11: classiication of solids

Source & Credit: Askiitians
Structure of Sodium Chloride
The structure of ionic crystals depends upon the structure and the size of their ions. Each ion is
surrounded by a certain number of ions of opposite charge. In the structure of NaCl each Na+ ion is
surrounded by six chloride ions. Fig (4.17) shows how these ions are arranged in the crystal lattice. It is
clear that Na+ has ten electrons while Cl- has total 18 electrons. The size of the Cl- is bigger than that of Na+
o
The distance between two nearest ions of the same kind i.e., Cl- ions is 5.63 A . So the
o
distance between two adjacent ions of diferent kind is 5.63/2 = 2.815 A .
37
Figs (4.17 a, b) The unit cell of sodium chloride showing that four NaCl formula units are present in a unit cell.
The location of Na+ and Cl- is such that each Na+ is surrounded by six Cl- placed at the corners
of a regular octahedron Fig. (4.17 a). So the coordination number of each Na+ is six. Similarly,
each Cl- is also surrounded by six Na+. Na+ and C1- are not connected to one another by pairs
because all six Cl- ions are at the same distance away from one Na+. It has been observed that
independent molecules of NaCl do exist in the vapour phase. Anyhow, in solid NaCl there
are no independent molecules of NaCl. That is why NaCl is said to have formula unit of NaCl.
While looking at the Fig.(4.17 b), we see that there are eight Cl- at the comers of the cube, and
each is being shared amongst eight cubes. l/8th part of each Cl- ion is considered for this unit cell.
So, one complete Cl- is contributed by eight corners. Similarly,six chloride ions are present at the
face centres and each is being shared between t wo cells. Thus.per unit cell there are 8/8 + 6/2 =
4 Cl- ions. You can justify the presence of 4 Na+ , if you take a unit cell having 8Na+ at eight corners
and 6Na+ at faces. So, there are equal number of Na+ ions, and therefore 4 NaCl units are present
per unit cell. Fig (4.17b)
Lattice Energy
Solids are composed of atoms, ions or molecules. However, many solids of daily importance
are ionic in nature. As mentioned earlier these ions exist in a three dimensional array which is
called as lattice.
38
When the oppositely charged ions are brought, close to each other energy is released. So
the lattice energy is the energy released when one mole of the ionic crystal is formed from
the gaseous ions. It is also deined as the energy required to break one mole of solid into
isolated ions in the gas phase. It is expressed in kj mole-1.
Na+ (g) + Cl − (g) → NaCl( s ) ฀ H = −787kJmole−1
Tables (4.8) Lattice energies

of ionic compounds
Ionic Lattice energy
compound (kJ/mol-1)
LiCl -833
NaF -895
NaCl -787
KCl -690
NaBr -728
KBr -665
Nal -690
Table (4.8) shows the lattice energies of many ionic compounds. It is clear from the table that
lattice energy decreases with the increase in the size of the cation keeping the anion same. It also
decreases with the increase in the size of anion. The reason in both cases is the same. With the
increase in the size of either cation or anion, the packing of oppositely charged ions becomes less
and less tight. The calculations related to the measurement of lattice energy will be discussed in
chapter seven.
4.7.2. Covalent Solids
Covalent solids are also called atomic solids, because they are composed of neutral atoms of
the same or of diferent elements. These atoms are held together by covalent bonds.
Covalent solids are of two types.
(i) Whenthecovalentbondsjointoformgiantmoleculeslikediamond,siliconcarbideoraluminiumnitride.
(ii) When atoms join to form the covalent bonds and separate layers are produced like that of
graphite, cadmium iodide and boron nitride.
39
Properties of Covalent Crystals
The bonding in covalent crystals extend in three dimensions. They contain a network of atoms.
The valencies of atoms are directed in deinite directions, so the packing of atoms in these crystals
is looser than those of ionic and metallic crystals. Thus covalent crystals have open structure.
These crystals are very hard and considerable amount of energy is required to break them.
They have high melting points and their volatility is very low.
Due to the absence of free electrons and ions they are bad conductors of electricity.
However, graphite has a layered structure and the electrons are available in between the layers.
These electrons are delocalised and conductivity becomes possible. Graphite is not a conductor
perpendicular to the layers.
Mostly covalent crystalline solids are insoluble in polar solvents like water but they are readily
soluble in non-polar solvents like benzene and carbon tetrachloride. The covalent crystals having
giant molecules like diamond and silicon carbide are insoluble in all the solvents. Because of their
big size, they do not interact with the solvent molecules. The chemical reactions of such crystalline
solids are very slow.
Let us try to understand the structure of diamond, which is a well known covalent solid.
Structure of Diamond
Diamond is one of the allotropic modiications of

carbon. It is best understood by taking into consideration
the number of electrons in the outermost shell of carbon,
which are four. The four atomic orbitals (one 2s and three
2p) undergo sp3 hybridization to give four sp3 hybridized
orbitals. They are directed in space along the four corners
of a tetrahedron Fig. (4.18 a).
This is the unit cell of diamond and a large number of
such unit cells undergo sp3-sp3 overlapping to form a huge
structure. Each carbon atom is linked with four other carbon
atoms. The bonds between carbon atoms are covalent
which run through the crystal in three-dimensions. All the
bond angles are 109.5° and the bond lengths are 154 pm.
40
The whole lattice is, therefore, continuous and because of the continuity of C-C covalent bonding,
the entire diamond crystal behaves as a huge or giant three-dimensional carbon molecule. This is
also called a macro-molecule.
Fig.(4.18b), The overall structure of diamond looks face centred-cubic Fig. (4.18 c)
Fig(4.18 c) face-centered cubic structure

of diamond
4.7.3. Molecular Solids
Those solid substances in which the particles forming the crystals are polar or non-polar
molecules or atoms, of a substance are called molecular solids. For instance, in solidiied noble
gases, there are non-polar atoms. Two types of of diamond intermolecular forces hold them
together.
(i) Dipole-dipole interactions.
(ii) van der Waals forces.
These intermolecular forces are much weaker than the forces of attraction between the
cations and the anions in ionic crystals, and between the atoms in the covalent crystals.
Ice and sugar are the best examples of crystals having polar molecules whereas iodine, sulphur,
phosphorus and carbon dioxide form the molecular crystals containing nonpolar molecules. Polar
molecular solids have usually higher melting and boiling points as compared to non-polar molecular
solids.
41
Properties of the Molecular Solids
X-ray analysis has shown the regular arrangements of atoms in constituent molecules of
these solids, and we get the exact positions of all the atoms.
The forces, which hold the molecules together in molecular crystals, are very weak so they
are soft and easily compressible.
They are mostly volatile and have low melting and boiling points. They are bad conductors
of electricity, have low densities and sometimes transparent to light. Polar molecular crystals are
mostly soluble in polar solvents, while non-polar molecular crystals are usually soluble in non-polar
solvents.
Iodine is one of the best examples of a molecular solid. Let us discuss the structure of iodine
molecule.
Structure of Solid Iodine
In the solid state the molecules of iodihe align in the form of layer lattice. This is shown in Fig
(4.19). I -I bond distance is 271.5 pm and it is appreciably longer than in gaseous iodine (266.6 pm).
As expected from its structure, iodine is a poor conductor of electricity.
Fig (4.19) Face centered cubic structure of iodine
42
4.7.4. Metallic Solids
In order to explain properties of

metallic solids various theories have been
proposed. A few of them are mentioned
here.
The irst theory of metallic bonding is
called electron pool or electron gas theory.
This theory was proposed by Drude and
extended by Loren (1923). According to
this theory, each atom in a metal crystal
loses all of its valence electrons. These
valence electrons form a pool or a gas.
The positively charged metal ions are
believed to be held together by electron
pool or gas. These positively charged ions
occupy deinite positions at measurable Fig (4.20) Positive ions surrounded by mobile electrons
distances from each other in the crystal
lattice. Valence elect rons are not attached to any individual ion or a pair of ions rather belong to
t he crystal as a whole. These electrons are free to move about from one part of the crystal to the
other. The force, which binds a metal cation to a number of electrons within its sphere of- inluence,
is known as metallic bond. The following Fig. (4.20) gives an idea of electron gas model.
L. Pauling has tried to explain the metallic bond according to valence bond theory. According to
this theory, the metallic bond is treated essentially as covalent in character. However, it is assumed
that the covalent bonds are not localized but are highly delocalized in metal structure.
Recently, molecular orbital theory was applied to explain the characteristics of metallic
solids. According to this theory, it is assumed that the electrons in the completely illed orbitals
are essentially localized, while atomic orbitals containing the valence electrons interact or overlap
to form a set of delocalized orbitals. These delocalized orbitals are the molecular orbitals which
extend over the entire crystal lattice. Such a combination of atomic orbitals produce as a large
number of closely spaced states. These states of energy are also known as bands of energy. That is
why it is also called a band theory. The energy gap between two bands determines the properties
of the metallic solids.
43
Properties of Metallic crystals
Metals are good conductor of electricity. When electric ield is applied between two ends of
a metal then the mobile electrons begin to move towards the positive pole and the new electrons
from the negative pole take their place Fig. (4.21a) Sometimes, the electrical conductivity of metals
decrease with the increase in temperature. The reason is that with the increase in temperature the
positive metal ions also begin to oscillate and the motion hinders the free movement of mobile
electrons between the positive ions. This hindrance decreases the electrical conductivity.
Fig (4.21a) Explanation of electrical conductivity of a metal
The rmal conductivity is another property associated with metallic solids. When a piece of
metal is heated at one end, the mobile electrons at this end absorb heat energy and move very
rapidly through the metallic lattice towards the cooler end. During the process they collide with
adjacent electrons and transfer their heat energy to them.
Whenever the metals are freshly cut, most of them possess metallic luster which means that
they have a shining surface. When light falls on the metallic surface, the incident light collides with
the mobile electrons and they are excited. These electrons when deexcited give of some energy
in the form of light. This light appears to be relected from the surface of the metal which gives a
shining look.
44
Metals are malleable and ductile whenever stress is applied on them. Their layers slip pass
each other. The structure of the metal changes without fracturing as shown in the Fig. (4.21b).
Fig(4.21b) Deformation of metal structures
Structure of Metals
In the previous article of metallic solids, we have

learnt that metal atoms are arranged in deinite pattern.
Free electrons are roaming about in the crystal lattice. So
a metal may be regarded as an assembly of the positively
charged spheres of identical radii which are packed
together to ill the space as completely as possible.
To understand the closed packing of atoms in metal
structures, let us suppose that the metal atoms are like
hard spherical balls. Take twelve spherical balls and pack
in a box as shown in Fig (4.22 a). Fig (4.22 a) Packing of twelve sphere in a box
(two dimensional view)
45
The spaces during the packing are larger. When the box
is shaken, the balls will rearrange as shown in Fig (4.22 b).
The arrangement of these balls are now stable and more
closely packed. It is the natural tendency of the balls to
have closely packed arrangement of eleven spheres after
shaking.
In order to understand,how various unit cells of the
crystal lattice are developed, consider three balls which
join together in one plane. The fourth ball is inserted in
the space created by the other three as a second layer.
Fig (4.22 b)Packing of eleven spheres in a box
In this way tetrahedral structure is obtained Fig (4.22 c). ( two dimentional view)
Actually, the fourth ball of the second layer is placed in
the depression created by the irst three balls. These depressions are also called interstices or
crevices or voids.
Consider the Fig (4.22 d) in which eleven balls of Fig. (4.22 b) are present in the irst layer
(circles with shade). The balls of the second layer (circle without shade) can it into the depressions
or interstices created by the irst layer. When the balls of the second layer are arranged, then all
the depressions of the irst layer are not occupied. There are two types of depressions as ‘a’ and
‘b’. The depressions marked ‘b’ are not occupied by the second layer and one can see the ground
from looking at the top through depressions ‘b’. The new depressions marked ‘a’ are created by the
second layer. Through the depressions ‘a’, we can not see the ground, but balls of the irst layer.
Now arrange the balls of third layer in the depression of second layer. When the balls of the third
layer are placed abov the second layer then there are two possibilities. Third layer balls may be
accommodated in ‘a’- type or ‘b’-type interstices or depressions.
Fig (4.22 c) The formation of a

tetrahedral site, due to four balls
Fig (4.22 d) Close packing of spheres, showing 11
balls in irst layer and 6 balls in second layer.
46
(i) Cubic Close Packing
When the atoms of the third layer it into the interstices marked b, then the atoms of the
third layer will not lie directly above those of the atoms of irst layer. This pattern of arrangement
is called ABC ABC-------------- or 123 123-----------------. It is named as face centred cubic arrangement
Fig. (4.23a). The balls of fourth, seventh and tenth layers will be in front of each other.
Fig (4.23 a) Cubic close packing or Fig (4.23 b) Hexagonal close packing (ABAB . . . )
Face centred cubic arrangement (ABCABC . . . )
(ii) Hexagonal Close Packing
When the atoms of the third layer are arranged in such a way that they occupy the depressions
created by the second layer i.e., in the ‘a’ types crevices then these atoms will directly lie above the
atoms of irst layer. This pattern of arrangement is usually written as ABAB ....... or 1212 . This
pattern has been named as hexagonal close packing Fig(4.23b). The balls of third, ifth, seventh
layers will be in front of each other.
Comparison of Properties of Various Types of Crystals
The following table gives a view to the comparison of properties of four types of crystals.
47
Table (4.9) Type of Crystalline Solids

Type of Structural Intermolecular Typical Properties Examples
Solid Particles Forces
Metallic cations plus metallic hardness varies from soft to Na; Mg; Al
delicalized bons Very hard; melting points Fe; Zn; Cu;
electrons varied from low to very high; Ag; W
lustrous; ductile; malleable;
very good conductors of heat
and electricity
Ionic cations and electrostatic hard; moderate to very high NaCl;NaNO3,
anions attractions melting points: MgO
nonconductors
of electricity (but good
electrical
conductors in the molten
state)
Molecular molecules Landon and/or soft; low melting points: noble-gas
(atoms of dipole-dipole nonconductors of heat and elements;
noble gases) and/or electricity; sublime easily CH4; CO2; P4
hydrogen bonds in many cases S8; I2; H2O
Network atoms covalent bonds very hard; very high melting C(diamonds);
covalent points: nonconductors of SiC; SiO2
elecrioity
48
4.8 Determination of Avogadro’s Number (NA)
Avagadro number can be calculated in a number of diferent ways. One of the most accurate
methods for determining this number is based on the study of crystalline solids.
In order to calculate this number, we need to know the volume of one gram-mole of a crystalline solid
and the distance between its atoms or ions in the crystal lattice.
The volume of one gram-mole of a solid can be calculated from its density while the spacing
between its atoms can be measured by X-rays.
The method of determining Avogadro’ s number is explained with a help of following solved exam-
ple which gives a reasonably good value of this number. The crystal of LiF is primitive cubic and can
be used to calculate the Avogadro’s number.
Example:
The density of LiF is 2.65 g cm-3. It is made up of cubic array of alternate Li+ and F- ions and the
o
distance between these ions is 2.01 A (2.01 x 10-8 cm). Calculate the Avogadro’s number.
Solution:
The formula mass of LiF = 6.939 + 18.9984

= 25.9374 g mol-1
Density of LiF = 2.65 g cm-3
From the density and molar mass, calculate the volume of 1 mole of solid LiF
The volume occupied

−1
25.9374g mol
by one formula unit of LiF =
2.65g cm −3
= .7889cm3 mol-1
49
From this volume, we can calculate the edge length of the cube. For this, we suppose that 9.788cm3
of LiF i.e., 1 mole of LiF, is present in the form of a cube. The cube root of this volume will give the
length of one edge of cube.
Edge length of the cube = 3
9.788cm3
= .1392cm
The number of ions of both Li+ and F- on one edge length can be calculated by dividing the edge
length by distance between ions. Hence, the number of (Li+and F- ) ions along one edge length
2.139cm
2.01 × 10−8 cm ion −1
=
= .064x10
1 8
When we take the cubes of these ions we get the total number of ions i.e. Li+ and F- in the cube.
Total number (Li+F-) of ions in the cube = (1.064x108)3

= .204x10
1 24
Since the cube of LiF crystal contains one Avogadro’s number of Li+ and one Avogadro’s
number of F- , so the Avogadro’s number will be
1.204 x108
=6.02x1023
2
50
KEY POINTS
1. Among three states of matter i.e. gases, liquids and solids, the intermolecular attractive forces
in the gases are negligible. In liquids intermolecular forces are strong enough to keep the
molecules close together. Anyhow, the molecules in liquids are free to move with respect to
one another. In solids the particles occupy speciic locations in three dimensional arrangement.
Molecules in liquids are free to move with respect to one another. In solids the particles occupy
speciic locations in three dimensional arrangement.
2. There are four types of intermolecular forces i.e. dipole-dipole forces, London dispersion forces,
hydrogen bonding and Ion-dipole forces. The relative strengths of dipole-dipole and dispersion
forces depend upon the polarity, polarisability, size and shape of the molecules. Hydrogen
bonding occurs in compounds containing 0-H,N - H, H - F bonds.
3. The vapour pressure of a liquid measures the tendency of a liquid to evaporate. It is the pressure
exerted by the vapours on the surface of a liquid when the rate of evaporation is equal to the
rate of condensation. A liquid boils when its vapour pressure equals the external pressure.
4. Many crystalline solids melt to give a turbid liquid before melting to give a clear liquid. These
turbid liquids possess some degree of order and are called liquid crystals. Liquid crystals have
the luidity of liquids and the optical properties of solids.
5. In crystalline solids the particles are arranged in a regular and repeating manner. The essential
structural features of a crystalline solid can be represented by its unit cell. The three dimensional
array of points representing atoms, ions or molecules is called crystal lattice. The points in the
crystal lattice represent positions in the structure where they have identical environments.
6. The simplest unit cell is a cubic unit cell. There are seven crystal systems overall.
7. The properties of solids depend on the arrangement of particles and the attractive forces
between them. Ionic solids are hard and brittle and have high melting points. Covalent solids
consist of atoms held together by covalent bonds and these bonds extend throughout the solid.
They are hard and have high melting points. Metallic solids consist of metal cations immersed
in a sea of electrons and give a wide range of properties. Molecular solids consist of atoms or
molecules held together by intermolecular forces.
8. The properties of solids depend on the arrangement of particles and the attractive forces
between them. Ionic solids are hard and brittle and have high melting points. Covalent solids
consist of atoms held together by covalent bonds and these bonds extend throughout the solid.
They are hard and have high melting points. Metallic solids consist of metal cations immersed
in a sea of electrons and give a wide range of properties. Molecular solids consist of atoms or
molecules held together by intermolecular forces.
51
EXERCISE
(QUESTIONS OF LIQUIDS)
Q1. Choose the best answers from the given choices.

(i) London dispersion forces are the only forces present among the
(a) molecules of water in liquid state
(b) atoms of helium in gaseous state at high temperature
(c) molecules of solid iodine.
(d) molecules of hydrogen chloride gas.
(ii) Acetone and chloroform are soluble in each other due to
(a) intermolecular hydrogen bonding (b) ion-dipole interaction
(c) instantaneous dipole (d) all of the above
(iii) NH, shows a maximum boiling point among the hydrides of Vth group elements due to
(a) very small size of nitrogen (b) lone pair of electrons present on nitrogen.
(c) enhanced electronegative character of nitrogen
(d) pyramidal structure of NH3
(iv) When water freezes at 0"C, its density decreases due to
(a) cubic structure of ice (b) empty spaces present in the structure of ice
(c) change of bond lengths (d) change of bond angles
(v) In order to raise the boiling point of water upto 110°C, the external pressure should be
(a) between 760 torr and 1200 torr (b) between 200 torr and 760 torr
(c) 765 torr (d) any value of pressure
Q2. Fill in the blanks with suitable words

(i) The polarizability of noble gases________down the group and results in the increase in
their boiling points.
(ii) ________ is developed in acetone and chloroform when they are mixed together.
(iii) Exceptionally weak_____of HF is due to strong hydrogen bonding present in it.
(iv) The concept of dynamic equilibrium is the ultimate _______of all reversible systems.
(v) ∆Hv of C6H14 should be_____ than that of C2H6.
(vi) During the formation of ice from liquid water there is a______ % increase in volume.
(vii) The rate of increase of vapour pressure of water_______at high temperatures.
(viii) A layer of ice on the surface of water____the water underneath for further heat loss.
(ix) Evaporation is a ________process.
(x) Liquid crystals are used in the display of_________ devices.
52
Q3. Indicate true or false as the case may be

(i) Dipole-dipole forces are weaker than dipole-induced dipole forces.
(ii) The ion dipole interactions are responsible for the dissolution of an ionic substance in water.
(iii) The high polarizability of iodine is responsible for its existence in solid form and its diference
from other halogens.
(iv) The strong hydrogen bonding in H2S makes it diferent from water.
(v) Hydrocarbons are soluble in water because they are polar compounds.
(vi) The viscosities of liquids partially depend upon the extent of hydrogen bonding.
(vii) The state of equilibrium between liquid state and vapours is dynamic in nature.
(viii) Heat of vapourization of liquids depend upon the intermolecular forces of attraction present
between their molecules.
(ix) Ice does not show any vapour pressure on its surface at -1oC.
(x) Boiling point of a liquid is independent of external pressure.
Q4 (a) What type of intermolecular forces will dominate in the following liquids.
(i) Ammonia, NH3 (ii) Octane, C8 H18 (iii) Argon, Ar
(iv) Propanone, CH3COCH3 (v) Methanol, CH3OH
(b) Propanone (CH3COCH3), propanol (CH3CH2CH2OH) and butane (CH3CH2CH2CH3) have
very similar relative molecular masses. List them in the expected order of increasing boiling points.
Explain your answer.
Q.5 Explain the following with reasons.

(i) In the hydrogen bonded structure of HF, which is the stronger bond: the shorter covalent
bond or the longer hydrogen bond between diferent molecules.
(ii) In a very cold winter the ish in garden ponds owe their lives to hydrogen bonding?
(iii) Water and ethanol can mix easily and in all proportions.
(iv) The origin of the intermolecular forces in water.
Q6 (a) Briely consider some of the efects on our lives if water has only a very weak hydrogen
bonding present among its molecules.
(b) All gases have a characteristic critical temperature. Above the critical temperature it is
impossible to liquefy a gas. The critical temperatures of carbon dioxide and methane are
31.14 0C and -81.9 0C, respectively. Which gas has the stronger intermolecular forces? Briely
explain your choice?
53
Q7 Three liquids have the properties mentioned against their names
Water Propanone Pentane

(i) Molecular Formula H2O C3H6O C5H12
(ii) Relativemolecularmass(a.m.u.) 18 58 72
Enthalpy change of
(iii) 41.1 31.9 27.7
vapourization (kJ mol-1)
(iv) Boiling point (0C) 100 56 36
(a) What type of intermolecular force predominates in each liquid?

(i) water (ii) propanone (iii) pentane
(b) What do you deduce about the relative strength of these forces in the liquids?
Justify your conclusions.
(c) If the liquids are shaken together in pairs,
(i) Which pair would be unlikely to mix?
(ii) Explain this immiscibility in terms of the forces between the molecules.
(iii) Choose one of the pairs that mix and say whether the enthalpy change on mixing
would be positive or negative.
Q8 Describe the various forces responsible for keeping the particles together in the following
elements and compounds and their efects on physical properties making use of the data
below.
Substance Formula Molar Mass (a.m.u.) M.P(°C)

Neon Ne 20 -248
Argon Ar 40 -189
Water H2O 18 0
Sodium luoride NaF 42 993
Diamond C 12 3350
Q9 The boiiing points and molar masses of hydrides of some irst row elements are tabulated
below:
Substance Boiling Point (K) Molar Mass (g mol-1)

CH4 109 16
NH3 240 17
H2O 373 18
54
Suggest reasons for the diference in their boiling points in terms of the type of molecules
involved and the nature of the forces present between them.
Q10 Explain the term saturated vapour pressure. Arrange in order of increasing vapour pressure:
ldm3 water, 1 dm3 ethanol, 50 cm3 water, 50 cm3 ethanol and 50 cm3 of ether.
Q11 While a volatile liquid standing in a breaker evaporates, the temperature of the liquid remains
the same as that of its surrounding. If the same liquid is allowed to vapourize into atmosphere
in an insulated vessel, its temperature falls below that of its surrounding. Explain the diference
in behaviour.
Q12 How does hydrogen bonding explain the following indicated properties of the substances?
(i) Structure of DNA (ii) Hydrogen bonding in proteins
(iii) Formation of ice and its lesser density than liquid water
(iv) Solubilities of compounds
Q13 What are liquid crystals? Give their uses in daily life.
Q14 Explain the following with reasons.

(i) Evaporation causes cooling.
(ii) Evaporation takes place at all temperatures.
(iii) Boiling needs a constant supply of heat.
(iv) Earthenware vessels keep water cool.
(v) One feels sense of cooling under the fan after bath.
(vi) Dynamic equilibrium is established during evaporation of a liquid in a closed vessel at
constant temperature.
(vii) The boiling point of water is diferent at Murree hills and at Mount Everest.
(viii) Vacuum distillation can be used to avoid decomposition of a sensitive liquid.
(ix) Heat of sublimation of a substance is greater than its heat of vaporization.
(x) Heat of sublimation of iodine is very high.
55
(QUESTIONS OF SOLIDS)
Q1. Multiple choice questions.
(i) Ionic solids are characterized by

(a) low melting points. (b) good conductivity in solid state,
(c) high vapour pressures. (d) solubility in polar solvents.
(ii) Amorphous solids
(a) have sharp melting points.
(b) undergo clean cleavage when cut with knife.
(c) have perfect arrangement of atoms.
(d) can possesses small regions of orderly arrangement of atoms.
(iii) The molecules of CO2 in dry ice form the
(a) ionic crystals (b) covalent crystals
(c) molecular crystals (d) any type of crystal
(iv) Which of the following is a pseudo solid?
(a) CaF2 (b) Glass (c) NaCl (d) All
(v) Diamond is a bad conductor because
(a) it has a tight structure (b) it has a high density
(c) there are no free electron present in the crystal of diamond to conduct electricity
(d) is transparent to light
Q2. Fill in the blanks

(i) In a crystal lattice, the number of nearest neighbours to each atom is called the_______.
(ii) There are__________ Bravis lattices.
(iii) A pseudo solid is regarded as__________liquid.
(iv) Glass may begin to crystallize by a process called__________ .
(v) Crystalline solids which exhibit the same _________ in all directions are called_________.
(vi) The branch of science which deals with the __________________ of crystals is called
crystallography.
Q.3 Indicate True/False as the case mav be

(i) There are ive parameters in unit cell dimensions of a crystal.
(ii) Ionic crystals are very hard, have low volatility and very low melting and boiling points.
56
(iii) The value of lattice energy of the ionic substances depends upon the size of ions.
(iv) Molecular orbital theory of solids is also called band theory.
(v) Ionic solid is good conductor of electricity in the molten state.
Q.4 What are solids? Give general properties of solids. How do you diferentiate between crystalline
solids and amorphous solids?
Q5
(a) Explain the following properties of crystalline solids. Give three examples in each case.
(i) Anisotropy (v) Polymorphism
(ii) Cleavage (vi) Transition temperature
(iii) Habit of a crystal (vii) Symmetry
(iv) Isomorphism (viii) Growing of a crystal
(b) How polymorphism and allotropy are related to each other? Give examples.
Q6
(a) Deine unit cell. What are unit cell dimensions? How the idea of crystal lattice is developed
from the concept of unit cell?
(b) Explain seven crystal systems and draw the shapes of their unit cells.
Q7
(a) What are ionic solids? Give their properties. Explain the structure of NaCl. Sketch a model to
justify that unit cell of NaCl has four formula units in it.
(b) What are covalent solids? Give their properties. Explain the structure of diamond.
(c) What are molecular crystals? Give their properties. Justify that molecular crystals are softer
than ionic crystals.
Q8
(a)Give diferent theories of a metallic bond. How does electron sea theory justify the electrical
conductivity, thermal conductivity and shining surfaces of metals?
(b) Explain with the help of a diagram
(i) Cubic close packing in the structure of metals.
(ii) Hexagonal close packing in the structure of metals.
Q9 Crystals of salts fracture easily but metals are deformed under stress without fracturing.
Explain the diference.
57
Q10 What is the coordination number of an ion? What is the coordination number of the cation in
(a) NaCl structure and (b) CsCl structure? Explain the reason for this diference?
Q11 Give examples of ionic solids, molecular solids and covalent macromolecular solids. What are
the factors which determine whether each of these types of solid will dissolve in water or not?
Q12 Explain the following with reasons:

(i) Sodium is softer than copper, but both are very good electrical conductors.
(ii) Diamond is hard and an electrical insulator.
(iii) Sodium chloride and caesium chloride have diferent structures.
(iv) Iodine dissolves readily in teterachloromethane.
(v) The vapour pressures of solids are far less than those of liquids.
(vi) Amorphous solid like glass is also called super cooled liquid.
(vii) Cleavage of the crystals is itself anisotropic behaviour.
(viii) The crystals showing isomorphism mostly have the same atomic ratios.
(ix) The transition temperature is shown by elements having allotropic forms and by
compounds showing polymorphism.
(x) One of the unit cell angles of hexagonal crystal is 120°.
(xi) The electrical conductivity of the metals decrease by increasing temperature.
(xii) In the closest packing of atoms of metals, only 74% space is occupied.
(xiii) Ionic crystals don’t conduct electricity in the solid state.
(xiv) Ionic crystals are highly brittle.
(xv) The number of positive ions surrounding the negative ion in the ionic crystal lattice
depends upon the sizes of the two ions.
58

CHP No 4

Uploaded by

Copyright:

Available Formats

CHP No 4

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CHP No 4

Uploaded by

Copyright:

Available Formats

CHAPTER

4 LIQUIDS AND SOLIDS

Animation 4.1: Solid, Liquid, Gas

4.1 INTERMOLECULAR FORCES

Anim ation 4.2 : Interm olecular forces

4.1.1 Dipole-dipole Forces

4.1.2 Dipole-induced Dipole Forces

Fig (4.2) Dipole-induced dipole interactions

4.1.3 Instantaneous Dipole-induced Dipole Forces or London Dispersion Forces

Fig. (4.3) Instantaneous dipole-induced

Anim ation 4.3 : London Dispersion Forces

4.1.4 Factors Affecting the London Forces

Polarizability is the quantitative Table(4.1) Boiling points of halogens and

Table (4.2) Boiling points and physical states of some hydrocarbons

4.1.5 Hydrogen Bonding

stronger than simple dipole-dipole

Anim ation 4.4 : hy drogen bonding

Fig (4.5) Hydrogen bonding between

The hydrogen bonding present in the

4.1.6 Properties and Application of Compounds Containing Hydrogen Bonding

1. Thermodynamic Properties of Covalent Hydrides

2. Solubility of Hydrogen- Bonded Molecules

The lower density of ice than liquid water at 0

4. Cleansing Action of Soaps and Detergents

5. Hydrogen Bonding in Biological Compounds and Food Materials

Fig (4.9 a) Hydrogen bonding

Fig (4.9 b) Hydrogen bonding in

6. Hydrogen Bonding in Paints, Dyes and Textile Materials

In order to understand evaporation, we have to examine the movement of molecules in liquids.

Anim ation 4.5 : Evaporation

4.2.1 Vapour Pressure

Fig (4.10) Evaporation of a liquid and establishment

The number of molecules leaving the surface is just equal

Vapour Pressure Increases with Temperature

4.2.2 Measuremerr of Vapour Pressure

Table (4.4) Vapour pressure of some

4.2.3 Boiling Point

Table (4.5) Boiling points of some

Fig (4.12) Vapour pressures(torr) of four common liquids shown as a

4.2.4 Boiling Point and External Pressure

4.2.5 Energetics of Phase Changes

Whenever, matter undergoes a physical change, it is always accompanied by an energy

(i) Molar Heat of Fusion (ΔHf)

(ii) Molar Heat of Vapourization (ΔHv)

(iii) Molar Heat of Sublimation (ΔHs)

4.2.6 Energy Changes and Intermolecular Attractions

Table (4.6) Heats of

4.2.7 Change of State and Dynamic Equilibrium

4.3 Liquid Crystals

In 1888, Frederick Reinitzer, an Austrian botanist discovered a universal property. He was

Uses of Liquid Crystals

4.4.1 Types of Solids

(i) Crystalline Solids

(ii) Amorphous Solids

4.4.2 Properties of Crystalline Solids

Isomorphs Crystalline form Atomic ratio

Polymorphism is a phenomenon in which a compound exists in more than one

Substance crystalline forms