States of Matter

Dr. Swati Keny

Asst Professor
Department of Pharmaceutics
PES’s Rajaram and Tarabai Bandekar College of Pharmacy
 States of Matter and properties of matter
• State of matter,
• changes in the state of matter,
• latent heats,
• vapour pressure,
• sublimation critical point,
• eutectic mixtures,
• gases, aerosols
• relative humidity,
• liquid complexes,
• liquid crystals,
• glassy states,
• solid -crystalline, amorphous & polymorphism.
 Matter
• Matter is substance that has a mass and takes up space.

• All matter is made of infinitely small atoms.

• These particles are in constant motion and therefore have kinetic

energy.

• The particles interact with each other by repulsions and attractions

and therefore also have a potential energy
 STATES OF MATTER
• Every substance in the universe is made up of a substance that can
exist in different forms called states.

• Almost all matter on Earth exists in three different states: solid,

liquid and gaseous.

• These states of matter have different properties.

• There is no clear demarcation between the different states and, in

many cases, a substance can exist in one of the three states. For
example, Ice, water and vapour.
 Classification of states of matter

States: Every substance in the universe is made up of a substance that can exist in different forms
called states.
Three states: Solid, Liquid and gases.
Eg: Ice, water and Vapor.
 Matter

Physical
Classification
Solids Chemical Classification
Liquids Pure substances
Gases (Elements and Compounds)
Mixture
(Homogenous and Heterogeneous)
 Solids
• Solids are rigid with defined shapes.

• Solids are a state where potential energies are much higher than
kinetics energies.

• The particles in a solid are moving but cannot pass through each other
because the attractions of neighbouring atoms or molecules are too
strong to overcome.

• As a result, all solids have a definite shape and volume and they can't be
compressed
 Liquids
• Liquids are less rigid than solids and are fluid.

• they are able to flow and take the form of their containers.

• Liquids have approximately equal kinetic and potential energies.

• This allows the atoms or molecules to move around each other but
remain in contact with each other.

• This result in Liquids having a defined volume, but an indefinite

form.
 Gases
• Gases are fluids, but unlike liquids, they can expand indefinitely.

• The kinetic energy in the gases is much higher than the potential
energy.

• The particles are very distant because of this higher kinetic energy.

• Therefore, a gas has no definite volume or shape.

• Gases move around, taking up all of the available space.(diffusion).

 Characteristics of different states of matter
SOLID LIQUID GAS
Maintains a fixed volume and Assumes the shape of the Assumes the shape and volume
shape part of the container it of container
Rigid - locked particles in place occupies The particles can move one
The particles can move / another
slide one another
Not easily compressible Not easily compressible compressible
Little free space between particles A lot of free space between the
particles
Does not flow easily Flow easily Flow easily
Rigid -particles cannot move or The particles can move The particles can move one
slide /slide one another another
Changes
in the
states of
Matter
 Chemical changes:

• A chemical change occurs when a substance changes into

something new.

• This happens because of heating, chemical reaction, etc.

• Chemical change indicated by if the density, melting point,

or freezing point of the original substance changes.
 Changes in state of matter
Description of Phase Change Term for Phase changes,
Liquid to gas Vaporization, which includes boiling and
evaporation
Gas to liquid Condensation
Solid to Gas Sublimation
Solid to liquid Melting
Liquid to solid Freezing
 Latent Heat
➢The amount of energy needed to melt or boil a certain amount of material is
called Latent heat.

➢Changes of state from solid to liquid or liquid to gaseous state and vice
versa………. Phase Changes.

➢Eg: Heat of freezing and the heat of vaporization.

➢The heat of freezing is the amount of thermal energy released in the case of
liquid freezing.

➢The heat of vaporization is the amount of thermal energy that must be needed
to transform a liquid into gas.
• Eg: Latent heat of vaporization of water : 540 Cal/g

• Latent heat of freezing of water : 80 Cal/ g

• Heat can be added or subtracted = Latent heat x Mass for a

phase change
• Q = Lh x M

• Q= Heat (Calories or Joules)

• Lh = Latent heat ( Calories/ gm or gm joules/gm)
• M= Mass in grams
 Melting or Fusion
• Melting or Fusion is the transition from a solid state to a liquid state.

• The temperature at which a solid melts is called its melting point.

• The different substances have different melting points.

• The melting point of the ice is 0° Celsius or 32 Fahrenheit.

• During heating the particles of the solid will start moving faster.

• Further continue to heat the solid. the particle will vibrate faster and faster.
 Melting or Fusion
• Finally, with sufficient heat, the movement of the particle will
become great enough to overcome the attraction that locks
the particles together.

• When this happen, the solid becomes a liquid.

• Hence more Energy is needed to change a solid to liquid.

 Freezing
• Freezing is the passage from a liquid to a solid state.

• freezing is the reverse of melting.

• substance freezes at the same temperature to which it

melts.

• Water freezes at 0° Celsius or 32 Fahrenheit.

 vaporization
• Vaporization is the change from a liquid state to a gaseous state.

• When a substance is heated. Its particle begin to go faster and faster.

• The faster particles are able to overcome the attraction of particles around them
and they release completely and become a gas.

• example: boiling water on the stove. as the water heats up, the steam rises
above the pan.
 Condensation
• Condensation is the transition from a gaseous state to a liquid state.

• As the gas cools. its particles starts slowing down.

• Condensation is the reverse of vaporization.

• The temperature at which a gas condenses is called its condensation point.

• Condensation occurs when the particles slow down so much that they cannot
overcome the attraction of surrounding particles.

• They gather together and form a liquid.

 LATENT HEAT OF FUSION (Lf)

❑Latent heat of fusion is associated with

the solid-liquid transition without change
in the temperature.

❑ For example, ice (at OOC or 32°F)

converts to water with the latent heat of
fusion.

❑Ice (at OOC) converts to water with the

latent heat of fusion.

.
❑ The heat of fusion for water at OOC is
approximately 80 calories per gram of ice
 Latent heat of vaporization(Lv)
• Latent heat of vaporization is associated with liquid-vapour
transition. The amount of heat required to convert unit mass of a
liquid into the vapour without a change in temperature.

• The latent heat of vaporization of water at 100°C is approximately

533 calories per gram of liquid.
 Vapour Pressure
➢The process by which molecules of a liquid go into the gaseous state
(Vapour) is called as Vaporisation or Evaporation

➢The reverse process of this is called as condensation or where gas becomes

liquid.

➢When the number of molecules escaping from liquid is equal to the number
of molecules returning to the liquid.

➢Rate of Evaporation= Rate of condensation.

➢Dynamic equilibrium is established
Liquid ⇌ Vapor
 Determination of Vapour Pressure
➢Static Method
 ➢Dynamic Method

Vapor pressure =m x RT
MV
 sublimation
• Sublimation is the process in which a solid converts to gas without passing
through the intermediate liquid state. Such materials are called sublime.
•
• This is due to the fact that if a solid can at some temperature exert a vapour
pressure equal to the external pressure.

• solid heated to this point, pass direct to vapour, and reverse changes will
occur on cooling the vapour. This is called true sublimation
 sublimation
• The sublimation curve represents
the vapour pressure curve of the
solid phase, the distillation curve and
the vapour pressure curve of the
liquid phase, the melting point curve
showing the temperature at which
the solid melts under increasing
pressure.
 Boiling Point
• If a liquid is placed in an open container and heated until the vapor pressure
equals the atmospheric pressure, the vapor will form bubbles that rise rapidly
through the liquid and escape into the gaseous state.
•
• The temperature at which the vapor pressure of the liquid equals the external
or atmospheric pressure is known as the boiling point.

• All the absorbed heat is used to change the liquid to vapor, and the
temperature does not rise until the liquid is completely vaporized.

• The atmospheric pressure at sea level is approximately 760 mm Hg

Effect of Vapour Pressure on Boiling point

The boiling point of the liquid

may be defined as the
temperature at which Vapour
pressure of the liquid equals
the atmospheric pressure
 PHASE: DIAGRAM
•A phase
diagram is a
representation
of the states of
matter, solid,
liquid, or gas
as a function
of
temperature
and pressure
• Critical point: It is the point at which the liquid-gas line ends. Beyond
this point, the liquid and gas phases become indistinguishable; they
merge into a single phase

• Triple point: The point at which the pressure and temperature at

which all three phases are present at equilibrium. At Triple point the
chemical potentials of all three phases are the same.

• Critical temperature: It is the temperature above which the liquid

state of a substance no longer exist regardless of pressure

• Critical pressure: it is pressure required to bring about liquefaction at

the critical temperature
AEROSOLS
• Gases can be liquefied under high pressure in a closed chamber as long as the
chamber is maintained below the critical temperature.

• When the pressure is reduced, the molecules expand and the liquid reverts to a
gas.

• This reversible change of state is the basic principle involved in the preparation of
pharmaceutical aerosols.

• In such products, a drug is dissolved or suspended in a propellant,

• Propellant is a material that is liquid under the pressure conditions existing

inside the container but that forms a gas under normal atmospheric conditions.
• Eg:Chlorofluorocarbons, hydro fluorocarbons ,nitrogen.
 Aerosols

• Aerosols are also called "Pressurized dosage forms

• Defined as system containing very fine solid particles or liquid droplets as

a dispersed phase and gas as dispersion medium or continuous phase.

• The aerosols upon actuation emit a fine dispersion of liquid and/ or solid
material in gaseous medium.
 AEROSOLS advantages

1. The formulation of pharmaceuticals as aerosols offers distinct advantages

over some of the more conventional methods of formulation.

2. Antiseptic materials can be sprayed onto abraded skin with a minimum of

discomfort to the patient.

3. Aerosols containing Ethyl chloride, sprayed on the skin, freezes the tissue
and produces' a local anesthesia and can be used in minor surgical
operations.

4. The pulmonary and nasal routes of administration enable higher rate of

passage into systemic circulation than does oral administration.
 Disadvantages of Aerosols:
• (a) Aerosols are costly systems.

• (b) Most of the propellants are toxic in nature. They may be harmful to body
and also pollute the nature.

• (c) A person may feel irritation on the injured skin due to cooing effect of
highly volatile propellants.

• (d) The formulation on aerosols is difficult to design especially when drug is

not soluble in propellant.
 Aerosol Principle:
• Aerosol consists of two parts, the
• product concentrate and
• the propellant.

• The product concentrates contain many additives like

• antioxidant,
• surfactants and
• Solvents and medications

• The propellant is usually a

• liquefied gas or
• mixture of liquefied gases
 Aerosol Principle:
• which may serve both the purpose of
• propellant and
• the solvent or vehicle for the product concentrate.

• When propellant is sealed within in aerosol container with the

product concentrate, an equilibrium is quickly established
between that portion of propellant which remains liquefied and
that which vaporizes and occupies the upper portion of the
aerosol container
 Aerosols
➢Basic principle in the preparation of Aerosols:- When
pressure becomes low, the molecules expand and the liquid
returns to gas.

➢Aerosol: Suspension of fine solid or liquid particles in gas.

➢Drug dissolved or suspended in a propellant.

➢Container designed to expel drug propellant due to over

pressure
 Aerosol Principle
• The vapour pressure exerts pressure on surface of the liquid
phase,
• The pressure upon actuation of the aerosol valve forces the
liquid phase in the dip -tube to the atmosphere through the
orifice of the valve.

• As the propellant meets the air, it immediately evaporates due

to the drop in the pressure, leaving the product
concentrate as air borne liquid droplets or dry particles,
depending upon the formulation.

• As the liquid phase is removed from the container, the

equilibrium is again established between propellants liquefied
and vapour state.

• Thus, the pressure is maintained constantly during the

expulsion of the product and hence the product may
continuously be released at the constant rate and pressure.
• I. Actuator: it is a button which activates the valve Valve assembly
assembly for the emission of the product when
pressed.
• II. Stem: It supports the actuator and delivers the
formulation.

• III. Gasket: The gasket serves to prevent leakage of the

formulation

• IV. Spring: It holds the gasket in proper place.

• V.Mounting cup: it is the part of aerosol container

which keeps valve in place.
VI. Housing: It is placed just below the mounting cup, serves as the link between the dip tube
and the stem and actuator.

VII. Dip tube: this tube is fitted to the housing and extended down into the product.
 Humidity is:
• A measure of the amount of water in the air
• Water is added to the air by the process of EVAPORATION.
 Relative Humidity
➢It is the ratio of the airs actual water content to its potential water
content at a given temperature.

Relative Humidity = Weight of Water Vapor in air

Weight of potential water vapour in air at
saturation

➢Expressed as percentage

➢Measured by hygrometer
 Factors that Affect Relative Humidity

1. Amount of water: If you increase the amount of

water in the air (by adding it due to evaporation),
Relative humidity will go up.

2. Temperature: Since warm air can hold more water

than cold air, if you lower the temperature the
Relative Humidity will go up, even if you don’t add
more water.
Water capacity of air at different temperatures
 Measuring Humidity

• Relative Humidity is measured using a PSYCHROMETER.

• A psychrometer is made of two thermometers. One is covered with a
wet cloth. When air moves over the wet cloth, evaporation occurs and
lowers the temperature on that thermometer. If you compare the
temperature on the two thermometers you can get the relative
humidity.
Determination of relative humidity

Ex. 1
Dry Bulb = 14 degrees C
Wet Bulb = 10 degrees C

Difference is 14-10 = 4

1st – look at dry bulb reading (14)

2nd – find difference (4)
3rd – RH is where they meet = 60%
 Gas
➢General Characteristics of Gases
✓Expansibility
✓Compressibility
✓Diffusibility
✓Pressure
✓Effect of heat Parameters of a gas
➢A gas can be described in terms of four parameters:
✓The volume, V of the gas
✓Pressure , P
✓Temperature, T
✓The number of moles, n of gas in the cylinder
 The gas laws
• The relationships which describes the general behaviour of gases are called as
the gas laws:-

➢Boyle’s Law

➢Charles Law

➢Gay Lussacs Law

➢Boyle’s Law
It states that: at constant temperature, the volume of a fixed mass of gas is
inversely proportional to its pressure. If pressure is doubled the volume is halved
V∝ 1/P (T, n are constants)
V= k x 1/P
Where k is the proportionality constant

PV= K

If P1V1 are the initial pressure and volume of a given sample of gas and P2V2 the
changed pressure and volume, we can write
P1V1 = k= P2V2

P1V1 = P2V2
➢Charles law
➢It states that : at constant pressure, the volume of a fixed mass of gas is
directly proportional to the kelvin temperature of absolute temperature. If
absolute temperature is doubled, the volume is doubled.

V∝ T ( P,n are constant)

V=Kt
K- Constant

If V1, T1 are the initial volume and temperature of a given mass of gas at
constant pressure and V2, T2 be the new values , We can write
V1/ T1 = k = V2 / T2
V1/T1= V2/T2
• The combined Gas law
• Boyles and Charle’s Law can be combined into a single relationship called the Combined gas
law

Boyle’s Law V ∝ 1/P Charle’s Law V ∝ T

(T,n constant) (P, n Constant)

• Therefore V ∝ T/P (n Constant )

• The combined gas law can be stated as: for a fixed mass of gas, the volume is directly
proportional to kelvin temperature and inversely proportional to the pressure.

• If k be the proportionality constant

V = K t/P (n constant)

PV / T = k (n constant)
• If the pressure, volume and temperature of a gas be changed from P1 V1 and
T1 to P2 V2 and T2 then

P1V1 / T1 = k

• P2 V2 / T2 = k

• P1 V1 / T1 = P2 V2 / T2
 Gay Lussac’s Law
➢1802- Gay Lusaac- Established a relationship between the pressure and
temperature. This is known as the Gay Lussac’s Law or temperature- pressure
law.
➢It states that: At constant Volume, the pressure of a fixed mass of gas is
directly proportional to the Kelvin temperature or absolute temperature.
➢Mathematically expressed as:
P T
P = Kt
Or P / T= k
For different conditions of pressure and temperature
P1 / T1 = k= P2 / T2
P1 / T1 = P2 / T2
Avogadro’s Law
➢Avogadro’s law can be stated as : Equal volumes of gases at the same temperature and
pressure contain equal number of moles or molecules. If the molar amount is doubled , the
volume is doubled.
V n
V = An

Where A is constant of proportionality

Or V/n=A
For any two gases with volumes V1, V2 and moles n1, n2 at constant T and P
V1 / n1 = V2 / n2
V1 = V2 n1 = n2
 Ideal Gas law
➢Three simple gas laws:
Boyle’s Law V∝ 1/P (T, n are constants)
Charle’s Law V∝T (P, n Constant)
Avogadro’s Law V ∝ n (P,T constant )

Three gas laws can be combined together into a single more general gas law:
V∝ nT/P ………….(Universal Gas Law/ Ideal gas law )

➢Ideal gas law may be stated as : the volume of a given amount of gas is directly proportional to the
number of moles of gas, directly proportional to the temperature and inversely proportional to the
pressure
V= Rn T/P
PV= nRT……. Ideal gas equation/ gas equation
R= Gas constant
 Dalton’s Law of Partial Pressure
➢The individual pressure of each gas in the mixture is defined as its Partial Pressure.

➢Dalton’s Law of Partial Pressure: It can be stated as the total pressure of a mixture of
gases is equal to the sum of the partial pressures of all the gases presents

➢Mathematically:
Ptotal = P1 + P2 + P3…………..(V and T are constant)
P1, P2, P3-------- Partial Pressure of the three gases 1, 2 and 3 and so on

Dalton’s Law of Partial Pressure follows by the application of the ideal-gas equation
P1= n1 (RT / V) P2= n2 (RT / V) P3= n3 (RT / V)
Pt = (n1+n2+n3) RT/V
Pt= nt RT/V
 Kinetic Molecular Theory of Gases
➢Maxwell and Boltzmann developed a mathematical theory to explain the
behaviour of gases and gas laws.

➢It is based on the fundamental concept that a gas is made up of a large number
of molecules in perpetual motion. Hence the theory is called the Kinetic
molecular theory.

➢Assumptions:
✓A gas consists of extremely small discrete particles called as molecules dispersed
throughout the container
✓Gas molecules are in constant random motion with high velocities.
✓The distance between the molecules are very large and it is assumed that van der waals
attractive forces between them do not exist
✓All collisions are perfectly elastic
✓The pressure of a gas is caused by the hits recorded by molecules on the walls
of the container

✓The average kinetic energy (1/2 mv2 ) of the gas molecules is directly
proportional to the absolute temperature (Kelvin temperature). This implies that
the average kinetic energy of molecules is the same at a given temperature

➢ How does an Ideal Gas differ from Real gases?

❖The real gases as hydrogen, Oxygen, nitrogen etc are opposed to the assumptions 1,2,3
stated above. Thus
❖The actual volume of molecules in an ideal gas is negligible, while in real gas it is
appreciable.
❖There are no attractive forces between molecules in an ideal gas while these exist in a real
gas
❖Molecular collisions in an ideal gas are directly elastic while it is not so in a real gas
 Liquefaction of gases- Critical Phenomenon
➢Critical Temperature, Tc, of a gas may be defined as that temperature above which it
cannot be liquefied no matter how great the pressure applied.

➢Critical Pressure, Pc, is the minimum pressure required to liquefy the gas at its critical
temperature.

➢Critical Volume, Vc, is the volume occupied by a mole of the gas at the critical temperature
and critical pressure,

➢Tc, Pc and Vc – collectively called as the critical constants.

➢Critical state

➢Critical phenomenon
 Andrews
isotherms of
carbon
dioxide
Faraday’s Method of liquefaction
Linde’s Method
Claude’s Method
Solid State

➢Solids-
Definite
Shape and
Volume

➢Can be
Crystalline or
Amorphous
➢4 types of crystalline solids
✓Ionic Solids
✓Molecular Solids
✓Covalent-Network Solids
✓Metallic Solids

➢Habbit of crystals: External shape is called the habit of the crystal

➢Plane surfaces of crystals are called Faces
➢The angles between the faces are referred to as the interfacial angles.
➢Symmetry of crystals
✓Plane of Symmetry
✓Axis of symmetry
✓Centre of symmetry
• The units that constitute the crystal
structure can be atoms, molecules, or
ions.

• The sodium chloride crystal, shown in

• Figure consists of a cubic lattice of

sodium ions interpenetrated by a lattice
of chloride ion, the binding force of the
crystal being the electrostatic attraction
of the oppositely charged ions.
 Polymorphism
• Some elemental substances chemically identical and exist in more than one
crystalline form and are said to be polymorphism.

• Polymorphs have different stabilities and may spontaneously convert from the
metastable form at a temperature to the stable form.

• They also exhibit different melting points, x-ray crystal and diffraction patterns
and solubilities,
 unstable

Low solubility High solubility

Low energy High energy
High melting point Low melting point

Stable metastable
X-ray Crystallography
Liquid Crystals
Solid Phase
• Molecules with both orientation and positional orders, and are held to each
other strongly
Liquid Phase
• Molecules with no orientation and positional orders, but are held together
by weak intermolecular forces
• Liquid Crystals :Molecules do not exhibit any positional order, but they do
possess a certain degree of orientational order
Gas Phase
• No ordering, no intermolecular attraction
 LIQUID CRYSTALS
• A phase that exists between solid and liquid
• Discovered in 19th century when studying a cholesterol derivative
 Liquid Crystal Phase
• A fluid phase in which a liquid crystal flows and will take the shape of its
container. It differs from liquid that there are still some orientational
order possessed by the molecules
Orientational Order
• Liquid crystals molecules possess orientational order.
this direction can be represented by an arrow 

• The direction of preferred orientation in a liquid crystal

is called the director.

• Order Parameter: To quantify how much order is

present in a material an order parameter (s) is defined.

• The order of parameter is given as follows:

• S = 1/2[3cos2θ- 1]

• Where θ is the angle made by each molecule with the

director.
THE LIQUID CRYSTALLINE STATE
• In the solid state the molecules are immobile, and
rotations are not as readily possible

• Structure of Liquid Crystals molecules in the liquid state

are mobile in three directions and can also rotate about
three axes

• The liquid crystalline state may result either from the

heating of solids (thermotropic liquid crystals) or from the
action of certain solvents on solids (lyotropic liquid
crystals).
 Criteria for a molecule being liquid crystalline
• The molecule must be elongated in shape-length should be
significantly greater than its width

• Molecule must have some rigidity in its central region

• The ends of the molecule are somewhat flexible

Typical representation of a LC molecule
 Types of Liquid Crystals

Thermotropic Liquid Crystals

• LC phase transitions resulted from temperature changes

Lytropic Liquid Crystals

• LC phase is formed when a molecule is dissolved in a suitable
solvent (with specific concentration at a particular temperature)
Different Liquid Crystal Phases (Mesophases.)

Nematic Liquid Crystal

• Derived from a Greek word for thread

• The simplest LC phase

• The molecules maintain a preferred

orientational direction as they diffuse
throughout the sample (in a fluid phase)
 Smectic Phase
• Besides orientation order, there also some positional order present in this phase

• Smectic A to K phases have been discovered

Smectic A phase:
Director perpendicular to the plane Smectic C phase:
director makes an angle with the plane
 APPLICATION OF LIQUID CRYSTALS IN PHARMACY
• Polymer liquid crystals have been extensively studied. They are found to be
the important phases to form super strength polymers for novel drug
delivery systems.

• Liquid crystals are also seen to be intimately involved in the functions of

biological structures such as living tissue

• Stability of emulsions can be improved due to smectic mesophase, which

possess high viscosity.

• Liquid crystal pharmaceuticals anti-tumor drug called Tolecine™, a

compound that has antiviral and antibacterial applications

• Liquid crystal thermography is the technique to evaluate inflammatory

conditions or describing viability of tissues
glassy state.
• As liquid is cooled from a high temperature, it may either crystallize (at
melting temperature(Tm) or become super cooled.

• On cooling below the Tm, their particles progressively lose translational

mobility, so that around the glass transition temperature (Tg) rearrangement
to regular lattice sites is practically unfeasible.

• this behaviour is different from the amorphous structures and termed as a

glassy state.
• Above Tm : In this segment, the polymer remains as a liquid whose viscosity
would depend on molecular weight and on the temperature of observation.

• Between Tm and Tg : This region may vary from crystalline to amorphous

depending on the polymer structural regularity and on experimental
conditions.

• Below Tg : The polymer material viewed as a glass is hard and rigid,

• In respect of behavioural pattern in terms of mechanical property parameters.

glassy state is closer to a crystalline solid than to a liquid

• In respect of molecular order the glassy state more closely resembles the
liquid.
 glassy state

• Quartz: solid state • Quartz: glassy state