UNIT- I

kiran
 CONTENTS

1. Intermolecular forces and states

of matter

Binding forces between molecules Eutectic mixtures

The states of matter Relative humidity
Change in the state of matter
The liquid state
Liquid crystalline state
Latent heat
Glossy state
Vapour pressure Solid state
Sublimation Amorphous
Critical point Polymorphism
2. Phase rule:

Definition and explanation

One component (water) system
Two component system (phenol-water system & TEA (Tri Ethyl Amine)
and water system)
1 – BINDING FORCES
BETWEEN MOLECULES
 INTRODUCTION
Atoms and molecules constitute most of the matter that is around us.
Every molecule or an atom exerts a force of attraction or repulsion on the other
constituents. This force is known as the intermolecular force. 
These forces are responsible for holding together of a substance. 
A chemical is usually considered as a collection of molecules. Each molecule is
further made up of two or more atoms. In short, the atoms are the building blocks
of matter.
Some types of forces between the atoms are responsible for joining them together.
These forces further act as binding forces between the molecules.
 Intramolecular forces- These are the forces between atoms within a single
molecule, which are strong.
Intermolecular forces- These are the forces between the molecules that hold
molecules, ions, and atoms together. Intermolecular forces are the forces between
molecules, and are generally weak.
Intermolecular forces are of 2 types:
1. Attractive forces:
These forces tend to attract the molecules towards each other.
These are of 2 kinds:
Cohesive forces: The attraction forces between like-molecules
Adhesive forces: The attraction forces between unlike-molecules
2. Repulsive forces:
These forces tend to repel the molecules from each other. Short range interaction.
These repulsive forces are necessary in order to prevent the molecules from
interpenetrating into one another.
The interaction between intermolecular forces may be used to describe how
molecules interact with each other.
The strength or weakness of intermolecular forces determines the state of matter of
a substance (e.g., solid, liquid, gas) and some of the chemical properties (e.g.,
melting point, structure).
(Additional info: An atom is made up of a nucleus of neutrons and protons ‐
even smaller particles than an atom. They are called subatomic particles. 
Electrons circle around this nucleus.)
 APPLICATIONS OF
INTERMOLECULAR FORCES
1) Properties of gases, liquids and solids: Properties such as density, viscosity,
boiling point and melting point, depend on the intermolecular forces. If the
intermolecular forces are stronger, the melting point of solids will be higher.
2) Interfacial phenomena: Surface tension, surface activity, adsorption of drugs on
solid and liquid surfaces etc., mainly depend on intermolecular forces. The higher the
cohesive forces of a liquid, the greater the surface tension. The higher the adhesive
forces, lesser will be the interfacial tension between two immiscible liquids.
3) Flocculation of suspensions: In flocculated suspensions, the insoluble solids exhibit
weak interparticle contacts or attractions. Such aggregation or flocculation of solids
provides an acceptable suspension.
4) Stabilisation of emulsions: Emulsions are prepared using two immiscible liquids
with the aid of emulsifying agents. These agents should have attractive forces with the
both aqueous and oil phases. The stronger the interaction, the greater the stability of the
emulsion. Thus good emulsion can be prepared.
5) Compaction of powders in capsules: If the intermolecular forces of the solids are
stronger, powders will have closed packing arrangement. Then capsules of the small
size will be sufficient for packing of such powders.
6) Compression of granules to form tablets: If intermolecular forces of solids are
stronger, less force is sufficient to compress granules into tablets.
FACTORS INFLUENCING
INTERMOLECULAR FORCES
The following factors influence the intermolecular forces:
Distance between molecules
Chemical nature of molecules
Spatial arrangement
i.) Distance between molecules:
Each molecule is surrounded by an electronic cloud (consists of groups of electrons)
around it.
When these molecules are close to each other, their electronic clouds interpenetrate.
As a result, the molecules experience repulsive forces.
These repulsive forces increase with decrease in distance.
At a distance of about 0.3 or 0.4 nm, the repulsive and attractive forces become
equal.
As the distance increases further, the influence of attractive forces between the
molecules will gets gradually increased, suppressing repulsive forces.
In gases, when intermolecular distance is moderate, the attractions are large.
- In liquids or solids, the repulsive forces tend to be higher and attractions are rather
weak.
ii.) Chemical nature of molecules:
Based on the chemical nature of molecules, intermolecular forces are
classified as follows:
a.)Van der Waals forces:
This type of interaction is weakly electrostatic (electrostatic force means
attraction or repulsion of particles or objects because of their electric charge) and the
bond energy is approximately 4.0 to 40 MJ/kmol. As a result, these substances usually
exist as liquids and gases.
- These forces are further classified into the following types:
Dipole-Dipole or keesome forces
Dipole-Induced dipole or Debye interactions
Induced dipole-induced dipole or London attractions
Dipole - Dipole forces:
There are two types of molecules based on the polarity.
The molecules that have separate positive and negative poles (2 poles) are called
polar compounds, also called dipole molecules.
The molecules that do not have such poles are called non polar molecules.
The dipole-dipole forces are the forces between polar i.e dipole molecules.
Dipolar molecules frequently tend to arrange themselves within the neighbouring
molecules, so that the negative pole of the molecule pints towards the positive pole
of the next molecule.
This type of interaction is called dipole-dipole force.
Ex: water, ethyl alcohol etc.
Dipole- induced dipole interactions:
In this type, the interaction is between dipole (polar molecule) and non polar
molecules.
Dipole or polar molecules tend to behave as a magnet and exert an electric field.
When a non polar molecule comes under the influence of the electric field of a
dipole, its charge distribution is unbalanced.
This results in the creation of positive and negative poles in the non polar
molecules, thus converting them into a polar compound i,e induced dipole.
Now the dipole and induced dipole interact effectively and these interactions are
called Dipole- induced dipole forces.
Ex: Interaction between h20 & o2 molecules.
Induced dipole-induced dipole interactions:
- In this type, the interaction is between two non-polar molecules.
- The electrons in a non polar molecule are considered to be in a constant motion.
- At any moment, there may be an imbalance of charge distribution in the molecule.
Thus a non polar molecule is self polarised (conversion of a non polar compound
into a polar compound is called polarisation).
- When a second non polar molecule collides with the induced-dipole, the non polar
molecule develops slightly negative pole at one end and positive pole at the other
end and gets transformed into a polar molecule (i.e induced dipole).
- Now these two (induced dipole and induced dipole) interact and such interactions
are induced dipole-induced dipole interactions.
- Ex: Hydrogen gas, benzene.
b.) Ionic type of interactions:
These are further classified into 2 types:
Ion-dipole forces
Ion-induced dipole forces
Ion-dipole forces:
(Explanation: Ions are of 2 types- Cation and anion. Cation is an ion with a
positive charge and anion is an ion with a negative charge)
In this type, the interaction is between ion and dipole molecules.
Cation (+) attracts the negative pole of the dipole.
Anion (-) attracts the positive pole of the dipole.
Ex: Solubility of Sodium chloride in water.
Ion-induced dipole forces:
In this type, an ion and a non polar molecule interact.
The non-polar molecule under the influence of an ion gets polarised.
Then the ion and the induced dipole molecule interact.
Ex: Interaction between iodine and sodium chloride.
c.) Hydrogen bonding:
In this type, the interaction is between molecules containing an electropositive
hydrogen atom and electronegative atoms such as fluorine, oxygen and nitrogen.
(Explanation: Here, bond formation happens by the exchange of the
electrons. The atom that donates the electron to form a bond is called
electropositive atom and the atom that receives the electron from the
electropositive atom is called electronegative atom. The hydrogen atom
always donates electrons for bond formation, so it is always electropositive).
The electronegative atoms take almost full possession of the electron cloud in the
molecule and become partially negative charged.
The small size of the hydrogen atom and its large electrostatic field makes it
moving closer to an electronegative atom.
Thus the electropositive hydrogen atom and the other electronegative atom get
strongly associated. Ex: Formation of ammonia.
Examples of Hydrogen Bonding:
a) Hydrogen Bonding in Hydrogen fluoride:
Fluorine having the highest value of electronegativity forms the strongest
hydrogen bond.

b) Hydrogen Bonding in Ammonia:

It contains highly electronegative atom nitrogen linked to hydrogen atoms.
c) Hydrogen Bonding in Water:
A water molecule contains a highly electronegative oxygen atom linked to
the hydrogen atom. Oxygen atom attracts the shared pair of electrons more
and this end of the molecule becomes negative whereas the hydrogen atoms
become positive.

d) Hydrogen Bonding in Alcohols:

Strength of the Hydrogen bond:
The hydrogen bond is a weak bond.
The strength of hydrogen bond is in-between the weak van der Waals forces
and the strong covalent bonds.
Properties of Hydrogen Bonding:
Solubility: Lower alcohols are soluble in water because of the hydrogen
bonding which can take place between water and alcohol molecule.
Volatility: As the compounds involving hydrogen bonding between different
molecules have a higher boiling point, so they are less volatile.
Viscosity and surface tension: The substances which contain hydrogen
bonding exist as an associated molecule. So their flow becomes comparatively
difficult. They have higher viscosity and high surface tension.
The lower density of ice than water: In the case of solid ice, the hydrogen
bonding gives rise to a cage-like structure of water molecules. As a matter of
fact, each water molecule is linked tetrahedral to four water molecules. The
molecules are not as closely packed as they are in a liquid state. When ice melts,
this case like structure collapses and the molecules come closer to each other.
Thus for the same mass of water, the volume decreases and density increases.
Therefore, ice has a lower density than water at 273 K. That is why ice floats.
d.) Hydrophobic interactions:
(Explanation: There are 2 types of molecules based on their attractive or
repulsive forces in respect to the water molecules. Hydrophobic molecules
are water hating molecules, which tend to repel from water molecules.
Hydrophilic molecules are water liking molecules, which tend to attract
towards the water molecules.)
The hydrophobic parts of the molecules have a tendency to avoid water
molecules, because these cannot form hydrogen bonding with water molecules
Hydrophobic molecules such as proteins form a micelle-like structure through
hydrophobic interactions.
The attraction of hydrophobic groups resulting from the water repulsion is known
as hydrophobic interaction.
It involves van der waals forces, hydrogen bonding and other interactions as
iii.) Spatial arrangement:
The interaction forces between molecules are contributed by the spatial
positioning of molecules.
These effects are also influenced by chemical nature of molecules.
Based on spatial arrangement, they are divided into following kinds:
a.)Molecular orientation:
When molecules with dipole attract each other, they orient themselves in a
manner that their positive poles are close to the negative poles of the other
molecules.
Ex: Water.
b.)Induction forces:
In non polar molecules, some type of attraction is essential to exist as molecules.
Therefore non polar molecules undergo induction (explanation: Induction
forces are the forces by which an ion or a dipole induces a non polar or no
dipole molecule into a polar or dipole molecule).
The extent of induction depends on the nature of molecules that get induced and
the nature of molecules that get induced and the nature of molecules that induce
dipoles.
c.)Dispersion forces:
Dispersion means uniform distribution of molecules.
These forces are mainly seen in non polar or low polarity molecules.
2 – STATES OF MATTER
 INTRODUCTION

Matter is all around us. Matter is the air you are breathing. Matter is the computer
you are reading from now. Matter is the stuff you touch and see. And it is more.
Matter is defined as anything that has mass and takes up space.
So what is matter made of? All matter is made of atoms. Atoms are the smallest
particle of matter. They are so small that you cannot see them with your eyes or
even with a standard microscope. A standard sheet of paper is about a million
atoms thick. Science has come up with a technology to identify atoms called a
scanning tunneling microscope (STM) which uses electricity to map atoms. There
is more about atoms later, but first let's learn about the three states of matter.
 Matter is made of molecules, atoms and ions. Matter exists in 3 states:
Gases
Liquids
Solids
Solids:
Matter that is composed of atoms packed tightly together are
known as solids. You cannot walk through a solid wall. The
matter is packed so tight that it prevents you from moving
through it. Solids hold their shape at room temperature. The
pencil that you left in the desk at school will still be the same
shape when you return tomorrow.
Even in solids there is a small space between the atoms.
Depending on how tight the atoms are packed determines the 
density of matter. This means that a one inch block of wood is
not as dense as a one inch block of gold. There is more space
between the atoms of the wood than the atoms of the gold.
Liquids:
Liquids do not hold their shape at 
room temperature. There is space between the
atoms of a liquid and they move slightly all of
the time. This allows you to stick your finger
into water and pull it back out, letting the
water fill back in where your finger once was.
But when walking through the water in the
swimming pool, you have to push the water
out of the way ‐ this means that you feel the
heaviness of the water. Liquids flow or pour
and can take on the shape of a container. If the
liquid is poured into a wider or narrower
container, the liquid will take on that new
shape. 
Gases:
Gases not only do not hold their shape at room temperature,
they don't even stay put. Gases are always moving. There is
so much space between the atoms in gas that you can move
around in them easily. When you walk from one side of the
room to the other, you have walked through a bunch of gases
that make up our air. You barely even know they are there.
Gases will take on the shape of their container and can be 
compressed into a smaller space. Like when we compress air
into a balloon ‐ it fills out the balloon shape. Gases will fill up
the space too. You don't see only half of the balloon filled
with air ‐ the air is not as influenced by gravity as a liquid or
a solid would be.
Change of State:
Matter can move from one state to another, but can still be the same substance. A
change of state, also called a phase change, is a physical change from one state of
matter to another, for example, from solid to liquid or from liquid to gas.
How does matter move from one phase to another? If the motion of the atoms is
altered by pressure or temperature, the state can change too. By lowering the
temperature of water, it can freeze into a solid. By heating water, it can become
steam which is a gas. Whether solid, liquid or gas ‐ water is still water.
Pressure can change matter from one state to another. Deep in the earth solids
turn to liquids because the heavy weight of layers and layers of the earth push
down on the solids causing them to turn to liquid magma. This is just one
example of how pressure can change matter too.
Other matter changes too, but often only exists in two states or requires the help
of humans and technology to move through all three phases. Water is the only
matter on earth that can be found naturally in all three - solid, liquid and a gas.
 GASEOUS STATE
Characteristics :
Highly Compressible: Gases are highly compressible. As the molecules in gaseous
elements are scattered at a large distance as compared to the other two states (solid
and liquid), these are highly compressible. The large intermolecular distance in the
gaseous state decreases with increasing *. Therefore this not only decreases their
volume but also brings the molecules closer to each other, thus reducing the gaps
between them and making gases highly compressible.
Low Density: When compared to liquids and solids gases show very low density.
As the intermolecular forces between the molecules are negligible, this state poses
a very low density. But the density increases with decreasing temperature and
increasing pressure.
Equal Pressure in All Directions: The molecules in a gaseous element show
similar behaviour. The molecules in a gaseous element scatter by forces in all
direction due to the negligible force of attraction between them. Therefore the
molecules exert pressure in all directions.
No Shape: The shape of LPG is like the shape of the gas tank that stores it! Gases
have no shape of their own. They take the shape of the container. The molecules
in gaseous elements exert pressure on the walls of the container and take the
shape of the container in which contains this gas.
Volume of the Container: Measuring the volume of a gas means measuring the
volume of the container. Their volume is the volume of the container. Since gas
scatters as soon as left loose, measuring the volume is impossible.
Mix Evenly: They mix evenly without the help of any mechanical change. The
gaseous elements are more susceptible to reactions and admixtures. The huge gap
between molecules gives the molecules of other elements an ease to mix with
each other. This property of gases makes them highly reactive chemical elements.
Intermolecular Forces: The intermolecular force between molecules of gaseous
elements is negligible. Hence these forces between the molecules in gas makes it
the most compressible state of matter. The various characteristics associated with a
gas also depend on the physical conditions faced by that gas. Hence in physical
conditions like temperature, pressure or density may have a contradicting effect
on a gases behaviour. At unchanged conditions, a gas follows an Ideal behaviour
but as the conditions start changing, gases deviate from their due behaviour.
Applications:
1) Anaesthetic gases- Certain anaesthetic agents are in vapour state at room
temperature. These gases are used to produce anaesthesia.
Ex: Cyclopropane, nitrous acid.
2) Sterilisation gas- Sterilisation is the process of removal of all viable forms of
microorganisms. Certain gases are used for sterilisation.
Ex: Ethylene oxide gas
3) Fuel gases: Gaseous fuels are more economical than solid fuels such as coal or
wood.
Ex: Propane, butane.
4) Gases in chemical processes: Gaseous reactants are used in chemical processes.
For example, hydrogen and nitrogen gases are used in the production of
ammonia.
5) Refrigeration gases: Some of the gases like propane are used as refrigeration
gases.
 IDEAL GAS EQUATION

Boyle’s law: For a given mass of gas at constant temperature (T), the pressure
(P) is inversely proportional to the volume (V).
P ∝ 1/V
Charles law: For a given mass of gas at constant pressure (P) ,the volume (V) is
directly proportional to the absolute temperature (T).
V∝T
Avogadro’s law: It states that one kilogram mole (n) of all gases under the same
conditions of temperature and pressure occupies the same volume (V).
V∝n
Ideal gas equation is derived from the equations of the above 3 laws.
According to Boyle’s law - V ∝ 1/P
According to Charles's law - V ∝ T
According to Avogadro’s law - V ∝ n
Combining the above 3 equations, we get
V ∝ nT/P
V = nRT/P
PV = nRT
The gases which obey the ideal gas equation are called ideal gases.
The gases which deviate from the ideal gas equation are called real gases or actual
gases.
DALTON’S LAW OF PARTIAL
PRESSURES

It states that the total pressure exerted by a mixture of ideal gases may be
considered as sum of the partial vapour pressures exerted by each of the ideal
gases, if alone were present and occupied the total volume.
Dalton’s law can be mathematically expressed as:
p = p1 + p2 + p3 + ………………
Where,
P = total pressure of the mixture of gases, kPa
p1 + p2 + p3 + ………etc = partial pressures of the gases 1,2,3,..etc ,
respectively, kPa
DIAGRAMMATIC REPRESENTATION
OF DALTON
 GRAHAM’S LAW OF
DIFFUSION OF GASES

It states that the rate of diffusion of a gas is inversely proportional to the square
root of its molecular mass.
It can be mathematically expressed as:
 VAN DER WAALS EQUATION

The van der waals equation is obtained by refinement of the ideal gas equation
incorporating appropriate pressure and volume corrections.
VAN DER WAALS EQUATION FOR
REAL GASES
3- CHANGES IN THE STATE
OF MATTER
 BASICS
The existence of matter in different states (i.e solid, liquid or gases) largely
depends on the temperature factor. In some conditions, even pressure also plays a
crucial role in changing the states of matter.

Vaporization: When temperature increases, the liquid absorbs heat. The

intermolecular forces become weaker and molecules escape individually into vapour.
This process is called vaporization. The required heat is designated as heat of
vaporization, when a change of state from liquid to gas is involved.
Ex: Anaesthetic ether becomes gas when the temperature is increased.
When heat is supplied to a liquid, vaporization takes place. This process
continues until the pressure exerted by the vapour is equal to the atmospheric
pressure.
Boiling point: Boiling point is defined as a temperature at which, the vapour
pressure of the liquid is equal to the atmospheric pressure.
Condensation: The conversion of matter from gaseous state to liquid state is
called Condensation.
Melting: Liquids can be obtained by heating the solids, in which molecules are
present in ordered manner and exhibit restricted movement. When solids are
heated, the molecules acquire sufficient energy to disrupt ordered arrangement
of the lattice and pass into liquid form. This process is called melting.
The temperature at which a liquid passes into a solid state is known as
freezing point. It is also known as melting point or fusion temperature.
 Fusion: The reverse phenomenon to melting is calledfusion, i.e, bringing liquid
molecules into close contact to form solid. In fusion, the change of matter takes
place from liquid state to solid state
Liquefaction: Certain gases can be converted into liquid state. Appreciable
interaction between the molecules in the gaseous state can be achieved by bringing
them together by the application of pressure. This process is called Liquefaction.
Once the pressure is released, the liquid again becomes gas.
Ex: Liquid petroleum gas, liquefied oxygen, liquefied carbon dioxide.
 LIQUEFACTION OF GASES
Liquefaction of gases means converting of gases into liquids. Its sequence of
steps involved in this process is described below.
Principles involved in liquefaction:
The principles of liquefaction can be studied under three headings.
a) Critical conditions
b) Joule-Thomson’s effect
c) Inversion temperature
a) Critical Conditions:
Liquefaction can be inferred as a transition from a gas to a liquid and
depends on temperature and pressure to which the substance is subjected. These are
critical conditions.
Critical temperature is defined as the temperature above which the liquid can no
longer exist as liquid.
Critical pressure is defined as the pressure required to liquefy a gas at its critical
temperature.
If a gas is cooled below its critical temperature, less pressure is sufficient to
liquefy it.
Critical pressure is also the highest vapour pressure a liquid can have.
In other words, as the temperature is increased sufficiently, a value is reached
above which it is impossible to liquefy a gas irrespective of the amount of the
pressure applied.
Molecules possess sufficient kinetic energy so that no amount of pressure can
bring them within the range of attractive forces that cause the particles stick
together.
Thus, the effect of temperature is more important than the pressure.
b) Joule-Thomson’s Effect:
When a gas is allowed to pass from a high-pressure zone to a low-pressure zone,
the gas expands by taking up heat from the surroundings, which ultimately results
in cooling.
Joule-Thomson's effect offers further support to the view that attractive forces do
exist between gas molecules.
As the gas expands, the molecules fall apart from one another. For this to occur
work has to be done to overcome the cohesive and attractive forces.
In this process, the kinetic energy of the gas decreases, since it is proportional to
temperature.
c) Inversion Temperature:
Experiments have shown that gases become cooler during Joule- Thomson's
expansion only if they are below a certain temperature known as inversion
temperature.
Inversion temperature is defined as the temperature characteristic of a gas below
which only the gas cools when allowed to get expanded.
At inversion temperature, there is no increase or decrease of temperature of the
surroundings.
Above inversion temperature, there is a small rise in temperature.
Below inversion temperature, there is a fall in temperature.
Applications of liquefied gases:
1) Liquid ammonia and liquid sulphur dioxide are used as refrigerants.
2) Liquid carbon dioxide is used in soda fountains.
3) Liquid air is an important source of oxygen in rockets, jet propelled planes and
bombs.
4) Compressed oxygen is used in welding.
 METHODS OF ACHIEVING
LIQUEFACTION
a) Faraday's method:
If gas is cooled, below its critical temperature, less pressure is sufficient to liquefy it.
Examples are sulphur dioxide, nitric oxide, chlorine etc.
The apparatus for Faraday's method consists of a V- shaped tube in one arm of which
the gas is produced while in the other, it is liquefied under its own pressure and with
the help of external cooling.
Hydrogen, oxygen and nitrogen gases cannot be liquefied by this method when the
pressure is raised at 270 MPa.
b) Linde's method:
Principle:
The principle used in this method is Joule- Thomson effect.
Air is liquefied based on the fact that a compressed gas on free expansion produced
intense cooling (Joule-Thomson effect).
At high pressure, the molecules of the gas are very close to each other and
molecular attractions are appreciable.
When it is allowed to escape through a jet into a region of low pressure, the
molecules move apart. In doing so the inter-molecular attraction must be overcome
and energy is needed for it.
This energy is taken from the gas itself, which is thereby cooled. This is called
Joule-Thomson effect.
Working:
In this apparatus, air is compressed to above 20 MPa and is allowed to pass
through a water-cooled pipe, where heat of compression is removed.
Then the compressed air is passed through a spiral pipe with a jet at the end
through which the air is issued.
The free expansion of gases at the jet results in a considerable drop in
temperature.
The cooled air now passes up and cools the incoming compressed gas of the
spiral tube.
Then it goes again to the compressor.
Thus on repeated compression and expansion, the temperature becomes low
enough to liquefy air.
c) Claude’s method:
Principle:
Compressed air is allowed to do mechanical work by expanding the cylinder of
an engine.
Here the cooling effect produced is greater than the Linde’s method as the gas
does work not only by owing the intermolecular forces, but also in driving the
engine.
The cooled gas is circulated around the coil carrying the incoming compressed
gas to produce intense pre-cooling.
Examples of gases that can be liquefied by this method are ammonia, heium,
nitrogen, air, chlorine, sulphur dioxide and oxygen.
Working:
The apparatus used for liquefaction by Claude’s method is shown in figure below.
Compressed gas is passed through a pipe, which bifurcates the pump.
A part of the gas goes into the expansion cylinder where it expands and does work
by driving the piston back and the gas thus gets cooled.
This gas goes up the liquefying chamber and cools down-coming compressed gas.
As a result, the released gas at the jet gets further cooled and liquefied.
Any gas escaping liquefaction goes back to the compressor and the whole
process is repeated over and over again.
4- LATENT HEAT
Definition:
The heat required to convert a solid into a liquid or vapour, or a liquid into a
vapour, without change of temperature.
The latent heat of fusion is the change from liquid to solid.
The latent heat of vaporization is from liquid to gas.
The latent heat of sublimation is the change from solid to gas.
Explanation:
Normally when heat energy is added to or removed from an object, the
temperature of the object changes; however, during phase changes, the
temperature of an object stays constant.
The temperature remains the same because energy is required for an object to
change phases.
Latent heat is the heat energy per mass unit required for a phase change to occur.
If we think about substances at a molecular level, gaseous molecules have more
vibration than liquid molecules.
So when you add heat to a liquid, you are actually causing the molecules to
vibrate.
 The latent heat is the energy required to change the molecular movement.
Each substance has a unique latent heat value.
So when you add heat to a liquid, you are actually causing the molecules to
vibrate.
Phase Changes by latent heat:
Boiling a pot of water is not as simple as just turning on the stove.
As you apply heat to the water, the temperature of the water increases until it
reaches 100 degrees Celsius, the boiling point of water.
The water will stay at this temperature until all of the water changes from liquid
to a gas.
During this process, you are continuing to add heat energy to the water, but the
water temperature does not increase. Where is this energy going? The answer lies
in the concept of latent heat.
To understand this concept of latent heat, we must first review phase changes.
Phase changes refer to a change in matter from one state to another.
The most familiar phase changes are seen in the different states of water, such as
freezing liquid water to create ice or boiling liquid water to create a gas.
As you can tell, heat plays a major role in changing matter from one phase to
another.
Formula for Latent Heat:
The formula for latent heat is:
Q = m * L
This equation relates the heat Q that must be added or removed for an object of
mass m to change phases. The object's individual latent heat is noted by L.
The unit of latent heat is J/kg.
The values of latent heat are variable depending on the nature of the phase change
taking place)
 Alternate explanation

Latent Heat:
When the change of state is studied carefully, we see that the temperature of a
substance remains constant during a change in the state! This is very strange. As if
the change in state opens up new portals or spaces where our supplied energy
hides. Therefore we call this hidden energy, the latent or the hidden heat. Let us
understand this with an example:
Suppose we have a block of ice we want to convert to water. We all know that ice
turns to water and vice versa at 0°C. Now assume we start heating ice at 0°C. You
will observe that when we do so, the temperature of ice does not change. It starts
converting to water but the temperature does not rise until the entire ice block has
been converted to water. But we are heating the ice block right? So, what
happened.
If a mass ‘m’ of any substance undergoes a change in state by absorbing an
amount of heat, Q at a constant Temperature T, then we have:
L = Q/m or Q = mL
All the heat supplied to the ice at 0 0C is used by the ice to change its phase from
solid to liquid. Thus the heat supplied is not used up to raise the temperature of
the substance.
 There are 2 kinds of Latent heat:
Latent Heat of Fusion:
The heat energy supplied per unit mass of a substance at its melting point to convert
the state of the substance from solid to liquid is known as Latent heat of Fusion.
Latent heat of Fusion of water is 334 Joules/gram of water.
Latent Heat of Vaporization:
The heat that a substance absorbs per unit mass at its boiling point to convert the
phase of the substance from liquid to gas is the Latent heat of Vaporization. Latent
heat of Vaporization of water is 2230 Joules/gram of water.
Now similarly, if you want to convert the phase of a substance from a gas to
liquid or from liquid to solid you need to cool the substance to its boiling point or
melting point as the conditions demand and then extract the amount of Latent heat to
facilitate the phase change.
5 - VAPOUR PRESSURE
Definition: Vapour pressure can be defined as pressure formed by the vapor of the
liquid (or solid) over the surface of the liquid. This pressure is formed in a
thermodynamic equilibrium state in a closed container at a certain temperature.
Explanation:
Consider a case of liquid confined in a closed container whose temperature is
maintained constant.
As in case of gases, molecules in the liquid state are also in random motion because
they posses certain amount of kinetic energy (due to thermal agitation).
Some molecules have higher kinetic energy (i.e., greater velocities) than others at
any moment.
Molecules with higher energies tend to escape from the liquid surface into the
vapour in the head-space. This is the vaporization process.
The rate of vaporization depends on the concentration of the molecules in liquid
state.
The average kinetic energy of the remaining molecules goes down." Hence, the
temperature of the liquid falls. For this reason, liquid on evaporation cools down.
At the same time, some of the molecules escaped into the vapour return to the
liquid. This is the condensation process.
The rate of condensation depends on the number of molecules (concentration)
present in the vapour state. These two processes continue simultaneously.
When the rate of evaporation is equal to the rate of condensation at a definite
temperature, vapour becomes saturated.
This is known as dynamic phase equilibrium, a state at which the number of
molecules leaving the surface is equal to the number of molecules returning to
it at a time at a given temperature. Similar to gases, the vapour also exerts
certain pressure.
Not all molecules have adequate kinetic energy so these remain in the liquid
phase.
When heat is supplied to the liquid, the kinetic energy of the molecules
increases and more number of molecules vaporize.
As a result, the vapour pressure increases continuously.
At a particular temperature, the vapour pressure is equal to the atmospheric
pressure. This temperature is known as boiling point of the liquid.
Vapour pressure of liquids are generally measured by two methods, barometric
method and isoteniscopic method).
Characteristics of Vapour Pressure:
A pure liquid experiences a greater amount
of vapour pressure as against a liquid’s
solution.
It is inversely proportional to the forces of
attraction existing between the molecules
of a liquid.
It increases with a rise in the temperature.
This is because the molecules gain kinetic
energy and thus, vapourise briskly.
 Alternative explanation`

All liquids exhibit tendency for evaporation.

Evaporation takes place at the surface of liquid.
If the kinetic energy of liquid molecules overcomes the intermolecular force of
attraction in the liquid state then the molecules from the surface of liquid escape
into space above surface. The process is called 'evaporation'.
If evaporation is carried out in a closed container system then the vapours of liquid
remains in contact with surface of liquid.
Like gas molecules vapour of molecules also execute continuous random motion.
During this motions, molecules collide with each other and also with the walls of
the container, losses their energy and returns back to liquid state. This process is
called as 'condensation'.
Evaporation and condensation are continues processes.
Hence, after some time an equilibrium is established, at constant temperature
between evaporation and condensation.
At equilibrium number of molecules in vapour state remains constant at constant
temperature.
"The pressure exerted by vapours of liquid on the surface of liquid when
equilibrium is established between liquid and it's vapour is called VAPOUR
PRESSURE of liquid.“
The vapour pressure of the liquid depends on the nature of the liquid and
temperature.
With increase of intermolecular force of attraction vapour pressure of liquid
decrease and with rise of temperature vapour pressure of liquid increases.
6- SUBLIMATION
Definition: Certain substances can directly pass from solid to gaseous state. This
process is called sublimation.
Ex: Camphor, iodine
Applications:
Sublimation and erosion cause ablation, a process which wears down glaciers.
Sublimation of iodine may be used to reveal latent fingerprints on paper.
Sublimation is used to purify compounds. It is especially useful for organic
compounds.
Because dry ice sublimates so readily, the compound is used to produce fog
effects.
Examples:
Dry ice is solid carbon dioxide. At room temperature and pressure, it sublimates
into carbon dioxide vapor.
Freezer burn results from sublimation of ice into water vapor.
At the right temperature, the elements iodine and arsenic will sublimate from
solid into gaseous form.
Naphthalene, a chemical commonly used in mothballs, readily sublimates at
room temperature and pressure.
Water ice will sublimate, although more slowly than dry ice. The effect may be
seen sometimes over snowfields when the sun is out, yet the temperature is cold.
7 - CRITICAL POINT
DEFINITION: The critical point or critical state is the point at which two phases of
a substance initially become indistinguishable from one another. The critical point
is the end point of a phase equilibrium curve, defined by a critical pressure T p and
critical temperature Pc. At this point, there is no phase boundary.

Critical temperature is defined as the temperature above which the liquid can no
longer exist as liquid.
Critical pressure is defined as the pressure required to liquefy a gas at its critical
temperature.
Explanation:

At the critical point, defined by a critical temperature Tc and a critical pressure,

the phase boundaries vanish. Example: The liquid-vapour critical point is the
most common example, which is at the end point of the pressure-vapour
temperature curve distinguishing a substance's liquid and vapor.
The meniscus between steam and water vanishes at temperatures above 374°C
and pressures above 217.6 atm, forming what is known as a supercritical fluid.
There is also a liquid-liquid critical point in mixtures, which occurs at the critical
solution temperature.
If a gas is cooled below its critical temperature, less pressure is sufficient to
liquefy it.
Critical pressure is also the highest vapour pressure a liquid can have. In other
words, as the temperature is increased sufficiently, a value is reached above
which it is impossible to liquefy a gas irrespective of the amount of the pressure
applied.
Molecules possess sufficient kinetic energy so that no amount of pressure can
bring them within the range of attractive forces that cause the particles stick
together.
Thus, the effect of temperature is more important than the pressure.
8- EUTECTIC MIXTURE
Definition:
A mixture of two or more substances in a particular ratio, which melts sharply
below the melting point of any individual component, and the temperature at
which the process happens is called eutectic point.
Below the eutectic temperature the mixture of the two substances will exist as a
solid. While above it the mixture will convert into a liquid.
Examples of eutectic mixture are:
1) Sodium chloride and water form a eutectoid when the mixture is 23.3% salt by
mass with a eutectic point at -21.2 °C. The system is used to make ice cream
and to melt ice and snow.
2) The eutectic point of the mixture of ethanol and water is nearly pure ethanol. The
value means there is a maximum proof or purity of alcohol that can be obtained
using distillation.
3) Eutectic alloys are used for soldering. A typical composition is 63% tin and 37%
lead, by mass
4) Eutectoid glassy metals exhibit extreme corrosion resistance and strength.
5) Inkjet printer ink is a eutectic mixture, permitting printing at a relatively low
temperature.)
6) Galinstan is a liquid metal alloy (composed of gallium, indium, and tin) used as a
low-toxicity replacement for mercury.
Factors governing eutectic mixture formation:
The components must be miscible in a liquid state & mostly immiscible in solid
state.
The components should have chemical groups that can interact to form physical
bonds such has intermolecular hydrogen bonding etc.
Applications:
Eutectic Mixtures are commonly used in drug designing and delivery processes
for various routes of administration.
For the identification of the compounds having similar melting points.
Local anesthetics in case of children (used topically)
9- RELATIVE HUMIDITY
Definition: It is a measure of the actual amount of water vapour in the air compared to
the total amount of vapour that can exist in the air at its current temperature.
Explanation:
Absolute humidity is a measure of the actual amount of water vapour (moisture) in
the air, regardless of the airs temperature. The higher the amount(weight) of water
vapour per kilogram, the higher the absolute humidity.
Relative humidity (expressed as a percent) measures water vapour, but relative to
the temperature of the air.
It is a percentage of how much moisture the air could possibly hold.
Warm air can hold more water vapour than cold air, so with the same amount of
absolute/specific humidity, cooler air will have a higher relative humidity, and
warmer air a lower relative humidity.
The amount of vapour that can be contained in the air increases with temperature.
The higher the percentage of relative humidity, the more humid (moist) the air
feels, while a lower percentage usually feels drier. 
Saturation occurs when air is holding the maximum amount of water vapour
possible at the existing pressure and temperature.
Saturation is equal to 100% relative humidity, resulting in precipitation).
ALTERNATIVE EXPLANATION

Absolute humidity is the measure of the actual water vapor in the air.
Relative humidity is the ratio of the current absolute humidity to the highest
possible absolute humidity (which depends on the current air temperature). 
Relative humidity tells us how much water vapor is in the air, compared to
how much it could hold at that temperature.
It is shown as a percent. For example, a relative humidity of 50 percent
means the air is holding one half of the water vapor it can hold.
Again, this is all dependent on the temperature.
Dew Point Temperature:
A graph that show maximum water vapor capacity
increasing as temperature increases.
If the amount of water vapor in the air stays the
same, but the temperature goes down, the relative
humidity will increase. This is because the colder
air cannot hold as much water vapor.
If the temperature gets cold enough, the air gets to
the point that it is holding the most water vapor it
can hold. The relative humidity for this
temperature would be 100 percent.
This is also known as the dew point temperature.
Why do you think they call it this? Think of what happens on cool nights. If
the temperature gets down to the dew point, some of the water vapor turns
back to liquid water – this is called condensation.
What do you see in the morning? That dew is just liquid water that has
condensed out of the air. It is the same thing that happens when you have a
cold glass of something and let it sit for a while – what happens to the outside
of the glass?
10 – THE LIQUID STATE
Characteristics:
Strong Intermolecular forces: The intermolecular force in a liquid are
stronger than a gas and weaker than a solid. The strong force of interaction
between the molecules is due to the less space shared by them at the molecular
level.
Definite Volume and density: Liquids have a definite volume. These unlike
gases occupy a limited space, the reason being their low space between the
molecules. Under normal physical conditions, the molecules of a liquid seldom
separate from one another. Not only are liquids denser than gases but are also
less compressible than them.
Free flowing and shapeless: Liquids take the shape of the container in which
they are stored. Due to the free-flowing molecules that move past each other
liquids assume the flowing characteristic as well.
 At normal conditions of temperature, pressure, and volume liquids generally,
show the above-mentioned features. When the physical conditions change the
basic characters of liquids also undergo a drastic change.
Apart from the above characteristics, liquids also show the following properties:
i) Boiling Point:
Liquids when heated evaporate.
In closed vessels, the heating produces vapors which exert pressure on the
container of the walls while when heated in open vessels, the vapors evaporate to
the surroundings from the surface.
When bulk vapors evaporate to the surroundings at a specific temperature, then
that temperature is called the boiling point. 
ii) Vapour Pressure:
Liquids show the unique property of turning into vapors, as soon as the
temperature rises!
Generally, vapors from the aqueous substance occupy the walls of the unfilled
part of the container and exert a pressure on the walls of that container, this
pressure is called the vapor pressure.
Initially, the vapor pressure increases but after some time it becomes constant.
Gradually, an equilibrium between the liquid phase and the vapor phase is
established. The vapor pressure at the point of equilibrium is known as the
equilibrium vapor pressure or saturated vapor pressure.
The whole phenomenon of vapor formation solely depends on the temperature
and hence tends to increase with the increasing temperature.
iii) Surface Tension:
liquids do not have a shape of their own, they take the shape of the container!
Despite its undefined shape, we know that the drop of any liquid looks like a
sphere. Why is it so? The answer is due to surface tension of liquids. Surface
tension is the property specific to liquids.
The molecules in a liquid experience an equal intermolecular force from all
the sides.
The intermolecular force between the molecules on the surface is exerted
perpendicularly downwards and this is called the surface tension of the liquid.
The surface tension of a liquid depends on the intermolecular forces directly,
greater the force higher is the surface tension.
 As compared to other molecules in the container, the surface molecules are the
most active and energetic.
Despite being less in number than the other molecules their pressure and energy
are high and hence exert a downward force towards the liquid.
Now if the surface is distorted and the surface of the liquid pulls another molecule
from the bulk, then it takes energy to rebuild the surface area.
The energy required to build the surface tension is called the surface energy.
iv) Viscosity:
The viscosity of a liquid substance is a measure of resistance to flow.
The intermolecular forces and internal friction between the moving molecules in
the liquids make them viscous to flow.
 The viscosity of the aqueous substance decreases with the increasing
temperature.
At high temperature, the force of attraction between the molecules decreases
and due to the high kinetic energy in the molecules the intermolecular forces
slip past each other in the layer.
This results in decreased viscosity.
Applications:
i) Liquids as solvents:
Liquids like water, glycerine, ethyl alcohol, chloroform, petroleum ether etc.,
can be used as vehicles for elixirs, syrups, injections etc.
ii) Liquids as drugs:
Some of the liquid preparations can be used as medications.
Ex: Clove oil used as antiseptic, methyl salicylate as counter-irritant, liquid
paraffin as purgative and peppermint oil as flavouring agent.
iii) Liquefied gases:
Some liquefied gases such as carbon dioxide, fluorochlorohydrocarbons,
hydrocarbons and petroleum gas are used as carbonated beverages, propellants,
refrigerants and fuel respectively.
11- LIQUID CRYSTALLINE
STATE
Explanation:
Materials in nature can be divided into different phases, also called states of matter,
depending on the mobility of the individual atoms or molecules.
The obvious states of matter are the solid, the fluid and the gaseous state.
In the solid state, intermolecular forces keep the molecules close together at a fixed
position and orientation, so the material remains in a definite shape.
In the fluid state, the molecules are still packed closely together, but they are able to
move around. Hence a fluid does not have a rigid shape, but adapts to the contours of
the container that holds it.
Like a liquid a gas has no fixed shape, but it has little resistance to compression because
there is enough empty space for the molecules to move closer. Whereas a liquid placed
in a container will form a puddle at the bottom of the container, a gas will expand to fill
the container.
Although the three categories seem very well defined, the borders between the different
states are not always clear.
Apart from the three familiar states, there exist a large number of other intermediate
phases. A simple example is a gel.
A gel is not quite solid, neither is it a liquid.
Liquid crystals are another important intermediate phase which exhibits features from
both the solid and the fluid state.
Liquid crystals have the ordering properties of solids but they flow like liquids.
Liquid crystals are the materials that are in many ways intermediate between the liquid
and solid states.
Liquid crystals exhibit different molecular arrangements than the liquid and solid states.
The liquid crystalline state combines properties of both liquid and solid states.
The liquid state is associated with the ability to flow, whereas the solid state is
characterized by an ordered, crystalline structure.
The liquid crystalline state may result either from the heating of solids or from the
action of certain solvents or solids.
Ex: 4-methoxylbenzylidene-4'-butylaniline (MBBA) transforms to liquid crystal at
20ºC, and to liquid at 74ºC.
For example, water can exist as a solid (ice), liquid, or gas (water vapor). The state
of water depends on its temperature. Below 0 C, water is a solid. As the temperature
rises above 0 C, ice melts to liquid water. When the temperature rises above 100 C,
liquid water vaporizes completely. Some substances can exist in states other than
solid, liquid, and vapor. Those are liquid crystals.
Substances that form liquid crystal structures are quite common.
Approximately 0.5% of known carbon compounds have liquid crystal states.
These structures are especially common in living organisms, where cell walls are
composed of molecules in a liquid crystal arrangement of parallel molecules in
layers.
A more mundane instance of liquid crystals is the opalescent fluid that forms in the
bottom of a soap dish.
Soap molecules have the appropriate oblong shape and, when mixed with a little
water, assume a liquid crystal arrangement.
“Liquid crystal” also accurately describes the arrangement of molecules in this
state.
“Liquid crystal” also accurately describes the arrangement of molecules in this state.
In the crystalline solid state, as represented, the arrangement of molecules is regular,
with a regularly repeating pattern in all directions. (Molecules of substances with a
liquid crystal state are generally oblong and rigid, that is, rod-shaped.). The
molecules are held in fixed positions by intermolecular forces.
As the temperature of a substance increases, its molecules vibrate more vigorously.
Eventually, these vibrations overcome the forces that hold the molecules in place,
and the molecules start to move.
In the liquid state, this motion overcomes the intermolecular forces that maintain a
crystalline state, and the molecules move into random positions, without pattern in
location or orientation
In materials that form liquid crystals, the intermolecular forces in the crystalline solid
are not the same in all directions; in some directions the forces are weaker than in
other directions.
As such a material is heated, the increased molecular motion overcomes the weaker
forces first, but its molecules remain bound by the stronger forces.
This produces a molecular arrangement that is random in some directions and regular
in others.
The molecules are still in layers, but within each layer, they are arranged in random
positions, although they remain more or less parallel to each other.
Within layers, the molecules can slide around each other, and the layers can slide over
one another.
This molecular mobility produces the fluidity characteristic of a liquid.
comparison
12 - GLOSSY STATE
13- SOLID STATE
Solids are formed when liquids are cooled. Solids consist of ions, atoms and
molecules, which are held in fixed positions and closely packed. The inter-particle
attractions in solids are stronger than in liquids.
Characteristics:
Definite shape, stiffness and rigidity.
Definite volume, due to close proximity of the molecules.
Definite melting point.
Practically incompressible, because molecules are very close.
Show elasticity to a certain extent and further fracture.
Slow diffusion, highly ordered with less freedom for movement.
Applications:
1) Drugs and exceipients (other additives included in the dosage forms) of interest
are employed in solid state, as crystals and powders.
2) Several dosage forms, such as tablets, capsules, dry syrups and dry powders for
injections, exist in solid state.
3) Fine powders are dispersed in liquids and used in injections and aerosol
formulations.
4) Formulations in solid state are easy to handle particularly for packaging and
transportation.
5) The physical properties of solids affect the biological activity of the finished
products.
6) Drugs in solid state are more stable, hence decomposition of drugs can be
prevented or reduced.
7) Solid state offers mechanical strength to metals. Hence these are used as materials
of construction of equipment for chemical processes.
CLASSIFICATION:
a) Based on the nature of bonds:
1) Metallic: Metallic bonding, examples are magnesium, copper and indium.
2) Ionic: Electrostatic forces of attraction, example is sodium chloride.
3) Valence (or atomic): Covalent bonding, example is diamond. Also van der Waals
forces between layers as in graphite.
4) Molecular: Weak van der Waals forces, example is naphthalene.
b) Based on the structure:
1) Crystalline:
Atoms, ions and molecules are arranged in a regularly repeated pattern.
These solids contain crystals in their structure and each crystal has definite
geometry. Adding further, as crystalline solids have low potential energy, they
are the most stable form of solids. 
Examples are metals, alloys, rocks and minerals.
Crystals can also be classified based -on the shapes namely, acicular, plate-
like, lameller etc.
Characteristics of Crystalline Solids:
Crystalline solids show regular structure and have definite geometrical shape
The sharp freezing point is found in crystalline solids. This is because the
distance between same atoms/molecules or ions is same and remains constant,
unlikely from amorphous solids
The heat of fusion is definite and fixed as the regularity in crystal lattice remains
same and is ideal
Crystalline Solids are also known as True Solids as they don’t tend to flow like
pseudo solids
When we cut a crystal solids with a knife, we obtain a flat and smooth surface
Uses of Crystalline Solids:
There are many applications of crystalline solids, some are:
Diamond is the most decent example of crystalline solids and is widely used in
making beautiful jewelry items
Quartz is extensively used in manufacturing of watches and clocks
Many crystalline solids are used as a raw material in many industries
2) Non-crystalline (or amorphous):
They do not have the characteristic regularity. Examples are glass, wood,
plastics and ceramics,
c) Based on the Physical properties:
1) Anisotropic:
A phenomenon of having physical properties different in different directions is
known as anisotropy.
Such solids are known as Anisotropic substances.
For instance, the velocity of light passing through a crystal varies with the
direction m which it is measured.
2) Isotropic:
A phenomenon of having Same physical properties in all directions is known as
isotropy.
The properties are index, mechanical strength, thermal and electrically
conductivity. Ex: Amorphous solids
Crystal habit of solids:
The crystals of a given substance may vary in size, relative development of faces,
number of faces and the kind of the faces present.
These changes are termed as crystal habit.
Crystal habit is the description of the outer appearance of a crystal.
Many drugs can exist in more than one crystalline form.
Crystal habit is important from a technology point of view, though significant
differences in the bioavailability (absorption) of drugs may not be exhibited.
Crystal habit influences the following ways:
(a) The ability to inject a suspension using a syringe needle. Plate-like crystals are
easier to inject than that of needle-like crystals.
(b) The flow properties and ease of compression.
 The habit of a crystal depends on the conditions of crystallization such as solvent
used, temperature, concentration and presence of impurities in the solution.
l. Supersaturation tends to transform a prism or a granule to a needle shape.
2. Cooling rate and agitation is effective in changing habit, since it changes the degree
of supersaturation. For example, napthalene gives thin plates, if recrystallized in
closed ethanol.
3. The crystallising solvent affects habit by preferential absorption on to certain faces
thereby inhibiting their growth. For example, resorcinol produces needless from
benzene and squat prisims from butyl acetate.
4. Addition of co-solvents, other solutes and ions may change habit by poisoning the
crystal growth in one or more directions. Sodium chloride is usually cubic, but urea
causes the sodium chloride crystal to have an octahedral habit.
14 - AMORPHOUS (UNDER
SOLID STATE)
 Amorphous solid, any noncrystalline solid in which the atoms and molecules are
not organized in a definite lattice pattern. Such solids include glass, plastic, and gel.
In other words, we can define amorphous solids as materials which don’t have
certain organized arrangement of atoms and molecules.
Most solids are amorphous in nature and are utilized in many sectors as well.
Characteristics:
The constituent particles of matter inside solid are arranged in a random manner,
that is, the position of atoms and molecules is not fixed and varies from one solid to
another.
Amorphous Solids don’t have definite shape or geometry due to random
arrangement of atoms and molecules inside the solid lattice.
Amorphous Solids are also called Pseudo-solids or Supercooled
Liquids because they don’t form crystalline structure and has the ability to flow
The nature of amorphous solids is isotropic in nature that is, the properties
measured in all directions come out to be same, example refractive index of
amorphous solids is same
Amorphous solids don’t show sharp melting point, this is because of irregular
packing of amorphous solids
When we cut an amorphous solid, we find the broken constituent particles to be
irregular in shape and geometry.
Amorphous solids are unsymmetrical in nature, due to irregular packing of
atoms and molecules inside the solid lattice
 Amorphous solids don’t have fixed heat of fusion because of absence of sharp
melting point.
Amorphous substances are high energy level molecules.
Examples: Plastics, Glass, Rubber, Metallic Glass, Polymers, Gel etc.
Uses:
The glass is widely used in packaging (food jars, cosmetics box, and soft-drink
bottles), making tableware (utensils), in the construction of buildings
( windows, lighting, and shelves) etc.
Rubber is mainly used in manufacturing of tires, footwear, ropes, camp cloth
and as a raw material for several industries
Use of polymer can be seen in manufacturing of pipes, medicines and as a
raw ingredient for many factories
Amorphous silicon is considered as the best photovoltaic material to convert
sunlight into electricity
15- POLYMORPHISM
(UNDER SOLID STATE)
 Polymorphism is the ability of a compound to crystallise as more than one
distinct crystalline species with different internal lattices.
Polymorphism is exhibited by 63% of barbiturates, 76% of steroids and 40% of
sulphonamides.+
A few examples are:
1) Chlorainphenicol palmitate - A Form, B Form, C Form etc.
2) Phenobarbitone - Form I, Form II, Form III etc.
Crystalline forms of spironolactone (diuretic, steroidal androsterone agonist)
exhibit different shapes and properties.
If an element crystallises as more than one distinct crystalline species, this
phenomenon is called allotropy.
For example, carbon exists as cubic, diamond or hexagonal graphite. Sulphur
exists in two forms, rhombic sulphur and monoclinic sulphur.
Since polymorphs differ in their melting points, the highest melting species is
generally the stable form.
By convention, polymorphs are designated by Roman numerical in their order of
stability at room temperature.
Form I usually has the highest melting point.
The other forms are further categorized as unstable (which readily converts into
stable form) and metastable (which slowly converts into stable form).
As different polymorphs arise through different arrangements of the molecules or
ions in the lattice, they will have different interaction energies in the solid state.
 Under a given set of conditions, the polymorph with the lowest free energy will be
the most stable and other polymorphs will tend to transform into it.
Polymorphs are structurally not different, but exhibit differences in their
physicochemical and biological properties. Some of them are:
 Melting point
 Solubility
 Dissolution
 Bioabsorption
Therefore the performance of different drugs depends on habit and crystalline
modifications of the active drugs.
Polymorphs are prepared by manipulation of conditions of crystallization such
as solvent, temperature and rate of cooling.
The metastable polymorphs are important in the formulation, but these slowly
convert into a stable form during storage of the product.
Such polymorphic transitions can also occur during milling, granulation, drying
and compression operations.
Consequently transformations can result in undesirable product performance.
Applications:
1) Enhanced solubility: Metastable forms have low melting points and high
solubilities. Therefore, they exhibit greater dissolution.
2) Improved dissolution : If solubility is enhanced, the dissolution rate also
increases. Metastable polymorph of methylprednisolone (Form II) has 1.4 times
higher rate of dissolution than stable form (Form I).
3) Enhanced absorption: As solubility and dissolution are enhanced, the rate of
absorption of metastable polymorph also increases. For example, metastable
methylprednisolone (Form II) has 1.7 times higher rate of absorption than a stable
crystal (Form I).
4) Manufacture of dosage forms: In the manufacture of dosage forms such as
suppositories, polymorphs like cocoa are used.
Pseudomorphism:
Pseudomorphs are defined as those solid forms, which arise because of
inclusion of small amounts of solvent of crystallization.
These are also known as solvates.
When water is the solvent of crystallization, the crystals are termed as hydrates.
Crystals that do not contain water are known as anhydrates. Ex: Ampicillin
exists as pseudomorphs.
The solvent plays a key role in holding the crystal together.
It may be part of a hydrogen-bonded network within the crystal structure.
These hydrates are very stable and difficult to dissolve in water. Ex: Glutethimide
exists as pseudomorphs.
Anhydrates have more aqueous solubility, dissolution and absorption than
hydrates, since they are high energy level molecules.
Isomorphism:
Isomorphism is the ability of forming crystals of similar shape by different
chemical substances.
Such substances are said to be isomorphs (the same shape).
Isomorphism is due to same chemical constitution. Examples are magnesium
sulphate, MgSO4.7H2O and zinc sulphate, ZnSO4.7H2O.
The property of isomorphous substances is the formation of mixed crystals.
For example, when solution of potash alum and chrome alum are mixed and
allowed to crystallize, a crop of pale violet crystals consisting of a homogenous
mixture of double salts is obtained.
16 - PHASE RULE AND
COMPONENT SYSTEMS
INTRODUCTION

A phase is defined as any homogeneous and physically distinct part of a system

bounded by a surface and is mechanically separable from other parts of the
system.
A phase may be gaseous , liquid or solid. It is perfectly homogeneous and distinct
from every other phase that is present in the system.
There must be a definite boundary between any two phases. This boundary is
known as the interface.
Air constitutes a single phase only as it contains a mixture of nitrogen, oxygen,
carbon dioxide, water vapour etc.,
A system consisting of only one phase is said to be homogeneous.
A mixture of two immiscible liquids such as water and benzene, will exist in two
distinct liquid phases and in addition there will be a vapour phase. Thus there will
be three phases each separated from the other by a well-defined bounding surface.
A system consisting of more than one phase is said to be heterogeneous.
When various phases are in equilibrium with one another in a heterogeneous
system, there can be no transfer of energy or mass from one phase to another.
This means that at equilibrium, the various phases must have the same
temperature and pressure and their respective compositions must remain constant
all along.
The homogeneous reversible reactions can be studied using the law of mass
action.
For heterogeneous reversible reactions , the phase rule given by Williard Gibbs is
used.
 PHASE RULE
Phase rule is a device for relating the effect of the least independent variables
(examples are temperature, pressure and concentration) upon the various phases that
can exist in equilibrium containing a given number of components.
It is known as Gibbs phase rule. Phase rule may be stated mathematically
F=C-P+2
F= number of degree of freedom
C=number of components
P=number of phases
Applications:
1) Phase rule can be applied in determining the purity of a pure solid, substance melts
at a constant temperature
2) Phase rule can be applied in the solubility phenomena.
Explanation of terms:
1) Phase (P):
A phase is defined as “ an homogeneous, physically distinct and mechanically
separable portion of system, which is separated from other such parts of the
system by definite boundary surfaces”
Example :
i) Liquid phase:
The number of liquid phase depends on the number of liquids present and their
miscibility.
If two liquids are immiscible, they will form two separate liquid phases.
Example : benzene and water.
 If two liquids are miscible they will form one liquid phase only. Example :
alcohol and water.
ii) Solid phase:
Each solid forms a separate phase.
The number of solid phase depends on the number of solids present in it.
Example : Many forms of sulphur can exist together, but these are all separate
phases.
iii) Gaseous phase:
Since a gaseous mixture are thoroughly miscible in all proportions, it will form
one phase only.
Example : a mixture of N2 and H2 forms one phse only.
iv) A solution of a substance in a solvent consists of one phase only.
Example: Glucose solution.
v) At freezing point, water consists of three phases:
Ice (s) Water (l) Water vapour (g)
vi) A homogeneous solid solution of a salt forms a single phase.
Example : Mohr’s salt [ FeSO4. (NH4)2SO4.6H2O] solution has a single phase.
2) Component (C):
The number of components is the smallest number of constituents by which the
composition of each phase in the system can be expressed in the form of a
chemical formula or an equation, at equilibrium.
Example :
i) In water system, The chemical component of all the three phases is H2O and
therefore it is one component system.
Ice (s) Water (l) Water vapour (g)
ii) Sulphur exists in four phases namely rhombic, monoclinic, liquid and vapour,
but the chemical composition of all phases is S. Thus is an one component
system.
iii) A system of saturated solution of NaCl consists of solid salt, salt solution and
water vapour. The chemical composition of all the three phases can be expressed
in terms of NaCl and H2O. Therefore it is a two component system.
3) Degree of freedom:
The 'degrees of freedom' of the system (at chemical equilibrium) refer to the
number of conditions or variables that can be altered, independent of each other,
without effecting the number of phases in the system.
Essentially, the degrees of freedom of a system describe the dependency of
parameters such as temperature and pressure on each other.
Example :
i) Consider the water system, Ice (s) Water (l) Water vapour (g)
 The three phases can be in equilibrium only at particular temperature and pressure.
Therefore, when all the three phases are present in equilibrium, then no condition
need to be specified.
The system is therefore zero variant or invariant or has no degree of freedom.
In this system if pressure or temperature is altered , three phases will not remain in
equilibrium and one of the phases disappears.
ii) Consider a system consisting of water in contact with its vapour,
Water (l) Water vapour (g)
To define this system completely, we must state either the temperature or pressure
Thus degree of freedom is one and the system is univariant.
iii) For a system consisting of water vapour phase only, we must state the values
of both the temperature and pressure in order to define the system completely.
Hence the system is bi-variant or has two degrees of freedom.
iv) For a gaseous mixture of N2 and H2, we must state both the pressure and
temperature, because if pressure and temperature are fixed, the volume
automatically becomes definite.
Hence, for a gaseous system, two factors must be stated in order to define it
completely and thus, it has two degrees of freedom or bi-variant system.
v) Consider a system consisting of ,
NaCl (s) NaCl-water (aq) Water vapour (g)
We must state either the temperature or pressure, because the saturation
solubility is fixed at a particular temperature or pressure. Hence the system is
univariant.
Merits of the Phase rule:
1. It is applicable to both physical and chemical equilibria.
2. It requires no information regarding molecular/microstructure, since it is applicable
to macroscopic systems.
3. It is a convenient method of classifying equilibrium states in terms of phases,
components and degrees of freedom.
4. It helps us to predict the behaviour of a system, under different sets of variables.
5. It indicates that different systems with same degree of freedom behave similarly.
6. It helps in deciding whether under a given set of conditions : a) various substances
would exist together in equilibrium (or) b) some of the substances present would be
interconverted or (c) some of the substances present would be eliminated.
Limitations of Phase rule:
1. It can be applied only for system in equilibrium. Consequently, it is of little value
in case of very slow equilibrium state attaining system.
2. It applies only to a single equilibrium system; and provide no information
regarding any other possible equilibria in the system.
3. It requires at most care in deciding the number of phases existing in an equilibrium
state, since it considers only the number of phases, rather than their amounts. Thus
even if a trace of phase is present, it accounts towards the total number of phases.
4. It conditions that all phases of the system must be present simultaneously under
the identical conditions of temperature and pressure.
5. It conditions that solid and liquid phases must not be in finely-divided state;
otherwise deviations occurs.
 ONE COMPONENT SYSTEM

The water system is a one component system.

Ice Water Vapour
(Solid) (liquid) (gas)
Each equilibrium involves two phases.
The nature of these phases which exist in equilibrium at any time depends on
the conditions of temperature and pressure.
These conditions have been determined and summarized in the pressure-
temperature diagram in which pressure is treated as independent variable and is
plotted along y-axis whereas temperature is plotted along x-axis.
The phase diagram for the water system is shown:
 Phase Diagram
Phase diagram is a graph obtained by plotting one degree of freedom against
another.
If the phase diagram is plotted between temperature against pressure, the diagram
is called P-T diagram. P-T diagram is used for one component system.
If the phase diagram is drawn between temperature against composition, the
diagram is called T-C diagram. T-C diagram is used for two component system.
Uses of Phase diagram:
1) From the phase diagram, it is possible to predict whether an eutectic alloy or a solid
solution is formed on cooling a homogeneous liquid containing mixture of two
metals. Used in testing purity of a liquid.
2) The phase diagrams are useful in understanding the properties of materials in the
heterogeneous equilibrium system.
3) The study of low melting eutectic alloys, used in soldering, can be carried out using
phase diagrams.
 The phase diagram consists of:
1.Curves : There are three curves OA, OB and OC.
2.Areas : Three curves OA , OB and OC divide the diagram into three areas AOB,
AOC and BOC.
3.Triple point : The above three curves meet at the point O and is known as triple
point.
1) Curve OA :
The curve OA is called vaporization curve. It represents the equilibrium between
water and vapour.
At any point on the curve the following equilibrium will exist.
Water Water vapour
The degree of freedom of the system is one, i.e, univariant.
Thus applying phase rule equation,
F=C–P+2=1–2+2;F=1
This equilibrium (i.e, line OA ) will extend upto the critical temperature ( 3740C).
Beyond the critical temperature the equilibrium will disappear only water vapour
will exist.
2) Curve OB:
The curve OB is called sublimation curve of ice, it represents the equilibrium between
ice and vapour.
At any point on the curve the following equilibrium will exist.
Ice Vapour
The degree of freedom of the system is one, i.e., univariant.
This is predicted by the phase rule.
F=C–P+2;F=1–2+2;F=1
This equilibrium line will extend upto the absolute zero(– 2730C ) where no vapour
can be present and only ice will exist.
3) Curve OC:
The curve OC is called melting point curve of ice, it represents the equilibrium
between ice and water.
At any point on the curve the following equilibrium will exist.
Ice Water
The curve OC is slightly inclined towards pressure axis.
This shows that melting point of ice decreases with increase of pressure.
The degree of freedom of the system is one. i.e., univariant.
Areas:
Area AOC, BOC , AOB represents water ice and vapour respectively.
In order to define the system at any point in the areas, it is essential to specify
both temperature and pressure.
The degree of freedom of the system is two. i.e., Bivariant.
This is predicted by the phase rule,
F=C–P+2
F = 1 – 1 +2
F=2
c) Triple point:
The three boundary lines intersect at a common point called triple point.
Triple point shows the conditions under which all three phases (solid-liquid-
vapour) can coexist in equilibrium.
The triple point is represented by:
Applying phase rule to one component (C=1) three phase (P=3)system gives:
F = C - P + 2 = 1 -3 + 2 = 0
The triple point has no degree of freedom. It means that three phases can coexist
in equilibrium only at a definite temperature and pressure. The values are
0.00750C and 4.58 mm respectively. At this triple point, neither pressure nor
temperature can be altered even slightly without causing the disappearance of
one of the phases.
Applications:
Deciding the portion of two liquids to be taken during formulation of solutions,
when a single liquid phase product is desirable.
Examples of partially miscible liquids used in pharmacy are: Water-aniline,
Carbon disulphide-methanol etc.
TWO COMPONENT SYSTEMS

We know the phase-rule equation,

F = C – P +2 ……… (1)
For a two component system, C = 2 and hence the above equation becomes,
F = 2 – P + 2 = 4 – P ……… (2)
The minimum number of phases in any system at equilibrium is one.
It is clear from the equation (2) , the maximum number of degree of freedom is
three.
Thus, three variables – pressure, temperature and composition of one of the
components must be specified to describe the system.
This will lead to three dimensional figures.
 Based on the solubility behaviour, curves may be studied under the following
examples of following 2 systems:
I) PHENOL-WATER SYSTEM
The miscibility pattern of phenol-water system is shown in figure below:
The left handed side of the parabolic curve represents the conjugate solution,
which depicts the percentage (w/w) of phenol in water at various temperatures.
As temperature increases, the solubility of phenol in water increases.
The right-hand side of the parabolic curve represents another conjugate solution,
which depicts the percentage (w/w) of warm in phenol at various temperatures.
These two curves meet at a maximum temperature.
This point on the curve corresponds to a temperature of 66.8 °C and the phenol
composition of 33% w/w.
At this temperature, the two conjugate solutions merge and only one layer results.
The critical solution temperature (CST) is defined as maximum temperature at
which the two conjugate solutions (layers) merge into one layer at all proportions.
This temperature is also known as upper consolute temperature. CST of phenol-
water system is 66.8 °C.
At any temperature above the critical solution temperature, phenol and water are
miscible in all proportions. A single layer of phenol and water is observed.
Outside the curves, phenol and water are miscible, i.e., one phase (or single layer)
is formed.
 Under the curve, normally liquids exist as two layers. Complete miscibility is
possible depending on the composition of the mixture.
On the line, the temperature represents miscibility temperature in that
composition. Both liquids give single layer.
The tie line is represented by the line drawn parallel to the base line from two
points on the curve at any temperature in the phase diagram of partially miscible
liquids.
Applications:
1) CST is a characteristic of a system and used for testing the purity of a substance.
2) This method can be used to determine the percentage composition of added
component in the conjugate solution.
II. TRIETHYLAMINE-WATER SYSTEM:
The temperature composition curve (mutual miscibility) of triethyl amine and
water is given below:
The left hand side of the curve indicates the miscibility of triethylamine in water.
The miscibility of triethylamine in water is decreased with increase in
temperature of the system.
The right hand side of the curve indicates the solubility of water in triethylamine.
The solubility of water in triethylamine is decreased with increase in temperature
of the system.
The two conjugate solutions mix.-up and become a single phage at and below
18.5 C (composition--50% triethylamine in water).
This temperature is called critical solution temperature or lower consolute
temperature.
Lower consolute temperature is defined as the minimum temperature at which
the two conjugate solutions (layer) are miscible in all proportions.
Miscibility at lower temperature is implicated as the formation of a single
compound from both components.
At any temperature below the lower consolute temperature, triethylamine and
water are miscible in all proportions. A single layer is obtained.
Outside the curves, triethylamine and water are miscible, i.e., one phase (or
single layer) is formed.
Above the curve, normally conjugate solutions exist as two layers.
 On the line, the temperature represents miscibility temperature at that
composition. Both liquids give single layer.
The equi-composition line (50-50) will be completely miscible at 10 °C. But at
50 °C, there will be separation of two layers.
Application:
This principle is applied in the preparation of paraldehyde. It consists of a
solution of paraldehyde in normal saline. Cooling this mixture during
preparation allows more rapid solution.
Influence of foreign particles on two-component systems:
The addition of a substance to a conjugate liquid system produces a ternary
system, i.e., it contains three components. The added substance may influence the
mutual solubility of liquid pair by two ways salting out (leading to phase
separation) or blending (leading to increased solubility).
If an electrolyte such as sodium chloride is added to the phenol-water system, the
critical solution temperature increases. This is because sodium chloride is more
soluble in water than in phenol. As a result, the solubility of phenol in water
decreases. This process is known as salting out.
Similarly, when naphthalene is added to the phenol-water system, the upper
consolute temperature increases. This is because napthalene is more soluble in
phenol than in water. As a result, the solubility of water in phenol decreases.
If the added substance is soluble in both liquids roughly to the same extent, the
mutual solubility of the liquid pair increases. This process is known as blending.
Hence, the-upper consolute temperature is lowered. The addition of succinic acid
to phenol-water system results such a phenomenon.
 PREVIOUS YEAR QUESTIONS
FROM UNIT – 1
2 Mark questions:

1) Define gas law.

2) What is eutectic mixture.

3) Define relative humidity

4) Write 2 examples of amorphous substances

5) Define Phase rule

6) What is Sublimation?

7) Write 2 applications of intermolecular forces in pharmacy.

8) What is a component? What is the number of components present in a mixture of

oxygen and nitrogen gases.

9) Define states of matter

10) What is hydrogen bond?

10 Mark questions:

1) Write about super critical fluid state with example

2) Explain a) Van der waals forces b)Hydrogen bonds

3) Add note on a) Liquid state & Liquid crystalline state b) Glossy state and Solid state

4) Describe principles widely used in liquefaction of gases and describe methods of

liquefaction of gases.

5) Write briefly on a) Crystalline solids b) Polymorphism

6) Explain the two component systems containing liquid phases.

7) Define Phase rule. Explain the phase equilibrium concept with phase diagram stating
the states of matter.

8) Discuss in brief, the factors affecting intermolecular forces.

9) State Gibb’s Phase rule. Explain the terms involved, with examples. Explain the phase
diagram of one component system with one example.

10) Explain Phase rule equation for two component systems.

11) Explain one component system for water.

12) Write about Phase eqillibria and Phase rule. Short note on binding forces between
molecules and their importance.
end