UNIT - 1

MATTER, PROPERTIES OF MATTER

Matter
• Matter is a general term describing any 'physical substance'.
• Matter is defined as anything that has mass and takes up space (it has volume). It
includes atoms and anything made up of them, and any particles (or combination of
particles) that act as if they have mass and volume.
• Matter, material substance that constitutes the observable universe and, together
with energy, forms the basis of all objective phenomena.
• All physical objects are composed of matter, and an easily observed property of
matter is its state or phase.
States of Matter
• Matter normally exists in one of the three states – solid, liquid and gas.
• The factors which usually determine the state in which matter exists are the intensity
of molecular forces, the temperature and pressure. Solid has the strongest
intermolecular force and gases have the weakest.
• As the temperature of solid is increased, the molecules acquire sufficient energy to
break the ordered structure and pass into liquid form. On further increasing the
temperature, the liquid change to gaseous state. Under certain conditions, substance
may be able to co-exist in all three states.
1. Solids:
• The molecules of solid are held together by strong bonds which impart a high melting
point to these substances.
• The structure may be crystalline and lattice-like or non-crystalline. However even a
non-crystalline solid have more order than liquid and gases.
• Solids have a definite shape, as well as mass and volume, and do not conform to the
shape of the container in which they are placed.
• Electrons of each atom are constantly in motion, so the atoms have a small vibration,
but they are fixed in their position.
• Because of this, particles in a solid have very low kinetic energy.
2. Liquids:
 • Particles are more loosely packed than in a solid and are able to flow around each
other, giving the liquid an indefinite shape. Therefore, the liquid will conform to the
shape of its container.
• When a gas is cooled, its kinetic energy decreases to a stage where the molecules
almost loose their kinetic energy and are not able to overcome the force of
attraction. As a result, gas convert to liquid.
• Liquifaction can also be brought by increasing pressure on gas. However pressure is
effective only below certain temperature. The temperature is called critical
temperature and can be defined as the temperature at which a gas cannot be
liquified even in very high pressure. The critical pressure is the pressure required to
liquify a gas at its critical temperature.
Note: The critical temperature of water is 374 °C and its critical pressure is 218 atm.
3. Gases:
• The physical behavior of gases is independent of chemical nature of molecules.
Therefore, almost all gases respond in an identical way to the variation in pressure,
temperature and volume.
• Since the molecules in a gas are always in a state of vigorous and rapid motion, these
travel in random paths, collide with one another and with the wall of container in
which they are confined.
• Gas can be compressed much more easily than a liquid or solid.
• When a gas is put under pressure by reducing the volume of the container, the space
between particles is reduced and the gas is compressed.
4. Plasmas:
• Plasmas are often considered to be fourth state of matter.
• Plasma consists of highly charged particles with extremely high kinetic energy.
• A plasma is a hot ionized gas consisting of approximately equal numbers of positively
charged ions and negatively charged electrons.
• Like gases, plasmas have no fixed shape or volume, and are less dense
than solids or liquids.
Changes in the state of matter
• Changing states of matter occur when matter loses or absorbs energy.
• When a substance absorbs energy the atoms and molecules move more rapidly and
this increased kinetic energy pushes particles far enough, that they change form.
• They are reversible changes and do not involve any changes in the chemical makeup
of the matter.
• Common changes of the state include melting, freezing, sublimation, deposition,
condensation, and vaporization.

• Freezing: Freezing is a phase transition in which a liquid turns into a solid when its
temperature is lowered below its freezing point.
• Melting: Melting, or fusion, is a physical process that results in the phase transition
of a substance from a solid to a liquid. This occurs when the internal energy of the
solid increases, typically by the application of heat or pressure, which increases the
substance's temperature to the melting point.
• Deposition: Deposition is a thermodynamic process, a phase transition in which gas
transforms into solid without passing through the liquid phase. The reverse of
deposition is sublimation and hence sometimes deposition is called desublimation.
• Sublimation: Sublimation is the transition of a substance directly from the solid to
the gas phase, without passing through the intermediate liquid phase.
• Vaporization: Vapourization of an element or compound is a phase transition from
the liquid phase to vapor.
• Condensation: Condensation is the change of the physical state of matter from gas
phase into liquid phase, and is the reverse of vaporization.
 • Latent Heat:
 In Latent heat, energy absorbed or released by a substance during a change in its
physical state (phase) that occurs without changing its temperature.
 The latent heat is normally expressed as the amount of heat (in units of joules or
calories) per mole or unit mass of the substance undergoing a change of state.
 Example: a substance condensing or vaporizing at a specified temperature and
pressure.
The latent heat of water at 0 degree Celsius for fusion is nearest to 334 joules per gram or
79.7 calories per gram.
On the other hand, the latent heat of water at 100°C for vaporization is approximately
2230 joules per gram or 533 calories per gram.
Vapor Pressure:
 The vapor pressure of a liquid is the equilibrium pressure of a vapor above its liquid
(or solid); that is, the pressure of the vapor resulting from evaporation of a liquid (or
solid) in a closed container.
Examples: water – 0.03 atm at 25C, diethyl ether – 0.7atm at same temperature.
 The vapor pressure of a liquid varies with its temperature.
 As the temperature of a liquid or solid increases its vapor pressure also increases.
Conversely, vapor pressure decreases as the temperature decreases.
Relative Humidity
Absolute Humidity:
Absolute humidity is defined as the measure of water vapour present per unit volume of
the gas under a given set of condition. Its unit is gram/m 3.
Saturation humidity (Saturated air):
• Humidity at saturated air represents the maximum possible amount of water vapour,
at a given temperature and pressure.
• Relative humidity a ratio, expressed in percent, of the amount of atmospheric
moisture present relative to the amount that would be present if the air were
saturated.
• Relative humidity is the amount of moisture in the air compared to what the air can
"hold" at that temperature.
Actual water vapour pressure
Relative humidity= saturated water vapour pressure * 100%

• For example if the air currently holds 30 grams of water vapor and the maximum it
can hold is 50 grams of water vapor, then the relative humidity is 60%.
Sublimation Critical Point:
  Sublimation is an endothermic phase transition of solid matter directly into gas
without it being converted into its liquid form. Sublimation critical point refers to the
maximum or minimum temperature and pressure beyond which the state of the
matter cannot be changed.
 The maximum temperature and pressure beyond which the state of the matter
cannot be changed.
 The temperature at which the vapor pressure of the solid phase of a compound is
equal to the total pressure of the gas phase in contact with it; analogous to the
boiling point of a liquid.
 The critical temperature of water is 374 °C and its critical pressure is 218 atm.

Eutectic Mixtures: (Eutectic-easy melting; Greek meaning)

 A eutectic mixture is defined as a mixture of two or more components which usually
do not interact to form a new chemical compound but, which at certain ratios, inhibit
the crystallization process of one another resulting in a system having a lower
melting point than either of the components.
 Eutectic mixtures, can be formed between Active Pharmaceutical Ingredients (APIs),
between APIs and excipient or between excipient; thereby providing a vast scope for
its applications in pharmaceutical industry.
 Certain substance such as menthol, thymol, camphor, phenol, salol etc. when mixed
in particular proportion tend to liquefy due to reduction in their respective melting
points. Mixtures of such substances are said to be eutectic mixtures.

Let us consider two substance A and B. As in figure, the points A and B represents melting
points of two components. As increasing quantities of B are added to A, the freezing point
of A falls along the curve C Similarly, as increasing quantities of A are added to B, the
freezing point of B falls along the curve BC. At the particular composition C, known as
eutectic point, the mixture of two substance has the lowest melting point. The composition
of two substances is known as eutectic mixture.The phenomenon of eutectic formation is
used in pharmaceutics to improve the dissolution behavior of certain drugs.
Eg. Aspirin-acetaminophen (37%-63%)
urea-acetaminophen (46%-54%)
Griseofulvin-succinic acid (55%-45%)

Gases:
 Gases are compressible fluid and has no definite shape.
 Owing to vigorous and rapid motion and resultant collisions, gas molecules travel in
random paths and collide not only with one another but also with the walls of the
container in which they are confined.
 Gas volume, is usually expressed in liters or cubic centimeters (1cm 3 = 1 ml).
Properties of gases:
• A sample of gas assumes both the shape and volume of the container.
• Gases are compressible.
• The densities of gases are much smaller than those of liquids and solids and are
highly variable depending on temperature and pressure.
• Gases form homogeneous mixtures (solutions) with one another in any proportion.

Gas laws:
5. Avogadro’s Law: The volume Amount Law (Amedeo Avogadro, 1811)
Gives the relationship between volume and amount when pressure and temperature are
held constant. Here, amount is measured in moles.
A mole (abbreviated mol) of a pure substance is a mass of the material in grams that is
numerically equal to the molecular mass in atomic mass units (amu). A mole of any material
will contain Avogadro's number of molecules.
For example, carbon has an atomic mass of exactly 12.0 atomic mass units -- a mole of
carbon is therefore 12 grams.
Avogadro’s Number: One mole always contains 6.022 × 1023 particles (atoms or molecules),
independent of the element or substance. A mole of any substance has a mass in grams
equal to its molecular mass, which can be calculated from the atomic masses given in the
periodic table of elements.
NA = 6.022 × 1023 mol−1
The Ideal Gas Law:
A combination of the laws presented above generates the Ideal Gas Law:
PV = nRT
Where,
P is pressure; V is volume; n is the number of moles;
T is temperature (K); R is the universal gas constant with a value of 8.31445 J/(mol∙K),
0.0821 Lit.atm/(mol.K), 8.2057 m3.atm/(mol.K), 62.3637 L.Torr/mol.K or L.mmHg/mol.K

Dalton’s law of Partial pressure: John Dalton, 1801

The total pressure of a mixture of gases is equal to the sum of the partial pressures of the
component gases.
PressureTotal = PressureGas 1 + PressureGas 2 +... PressureGas n

Aerosols – Inhalers
• Aerosols are the system that depends on the power of a compressed gas or
liquefied gas to expel the contents from the container with special valve system.
• Inhalers are often used to treat chronic obstructive pulmonary disease (COPD). They
are three types: Metered-dose inhaler, Dry powder inhalers, Nebulizers.
Principle
When a liquefied gas propellant or propellant mixture is sealed within an aerosol container
with the product concentrate, equilibrium is quickly established between the portion of
propellant that remains liquefied and that which vaporizes and occupies the upper portion
of aerosol container.
The vapor phase exerts pressure in all direction – against the walls of the container, the
valve assembly and the surface of the liquid phase, which is composed of the liquefied gas
and the product concentrate.
It is this pressure that upon actuation of aerosol valve forces the liquid phase up the dip
tube and out of the orifice of the valve into the atmosphere.
As the propellant meets the air, it expands and evaporates because of the drop in pressure,
leaving the product concentrate as liquid droplets of dry particles, depending upon the
formulation.
As the liquid phase is removed from the container, equilibrium between the propellant
remaining liquefied and that in vapor state is reestablished.
Thus, even during expulsion of the product from the aerosol package, the pressure within
remains virtually constant, and the product may be continuously released at an even rate
with same proportion.
Propellants used:
-Fluorocarbons
(Trichloromonoflouromethane, CCl3F)
(Dichlorodiflouromethane, CCL2F2)
-Hydrocarbons
(Propane, Isobutane)
-Compresses gas
Argon, nitrogen, carbon dioxide
SOLID STATE
CRYSTALLINE SOLIDS:
• A crystal or crystalline solid is a solid material having (such as atoms, molecules, or
ions) spontaneous arrangement of the particles into a repetitive orderly array, i.e.,
regular geometric patterns.
• Crystalline solids have definite shapes and orderly arrangement of units.
• They are incompressible and shows definite melting point.
• Examples are sodium chloride, urea, benzyl penicillin and aspirin.
• Crystalline form have low solubility and dissolution. Thus are used to produce
sustained release products.
 • Example is protamine zinc insulin suspension for injection.

Crystalline solids are divided into seven distinct forms.

The units that constitute the crystal structure are ions, atoms or molecules.
Ions with opposite charges are bonded together by electrostatic attractions as in the
crystals of sodium chloride.
Atoms are bonded together by covalent bond as in case of diamond and graphite.
Molecules are held together are held together by van der walls force and hydrogen
bonding. Examples are naphthalene and p-hydroxyl benzoic acid.
AMORPHOUS SOLIDS:
• Amorphous solids have no specific shape (Greek: amorphe means without form).
• The structural units are arranged randomly in the solid.
• These do not have definite melting points.
• Examples are glass, plastics, polymers, gel, novobiocin.
• Amorphous form of a compound is always more soluble than the corresponding
crystalline form. Thus it may exhibit better therapeutic effect than crystalline form.
• It is not always possible to determine the solids as crystalline or amorphous by casual
observation.
• For example: beeswax and paraffin although appear to be amorphous assume
crystalline arrangements when heated to cool slowly

Polymorphism
• Polymorphism is the ability of solid materials to exist in two or more crystalline forms
with different arrangements or conformations of the constituents in the crystal
lattice.
• These polymorphic forms of a drug differ in the physicochemical properties like
dissolution and solubility, chemical and physical stability, flowability and
hygroscopicity.
• Certain drugs can exist in more than one crystalline form. Such a phenomenon is
called polymorphism.
• About 63% of barbiturates, 67% of steroids and 40% of sulphonamides exhibit
polymorphism.
• Although the drug is chemically indistinguishable in each form, polymorphs differ
significantly with respect to a number of properties such as density, melting point,
solubility and dissolution rate.
Metastable polymorphs:
• These polymorphs slowly convert into stable polymorphs. If the rate of conversion is
so slow as to be negligible during the expected life of a drug product, metastable
polymorphs are preferred because of their unique physiochemical properties.
• The metastable polymorphs have lower melting points, higher solubility and higher
dissolution than their stable polymorphs. Therefore these are preferred in the
production of dosage forms.
• For example, riboflavin can exist in three different crystalline forms, which vary in
water solubility at 25°C from 60 mg per liter to 1.2 g per liter. The increased solubility
of metastable polymorph ordinarily results in increased dissolution and absorption.
Stable polymorphs: These are employed when metastable polymorphs are not suitable on
account of rapid decomposition.

Liquid Complexes
• Complex fluids are material intermediate between conventional liquids and solids,
displaying fluid like as well as solid-like behavior.
• binary mixtures having a coexistence between two phases: solid–liquid (suspensions
or solutions of macromolecules such as polymers), solid–gas (granular), liquid–gas
(foams) or liquid–liquid (emulsions).
• Liquid + solid = sol (colloid)
• Liquid + gas = bubbles, foams
• Liquid + liquid (immiscible) = emulsion
• Gas + liquid = drops, jets (Sprays)
• Gas + Solid + liquid = Granulation

Liquid Crystals
• The three distinct states of matter as solid, liquid, and gas have been discussed so
far. However, there is a state of matter, which does not meet the necessary
requirements of any of these three categories.
• Liquid crystals are matter in a state that has properties between those of
conventional liquid and those of solid crystals.
• For instance, a liquid crystal may flow like a liquid, but its molecules may be oriented
in a crystal-like way.
• For example, a substance like cholesterol or mayonnaise is somewhere between a
liquid and a solid. It is often called a mesomorphic state which is state of matter in
which the degree of molecular order is intermediate between the perfect three
 dimensional, long-range positional and orientational order found in solid crystals and
the absence of long-range order found in isotropic liquids, gases, and amorphous
solids. It is also called as meso intermediate.
• Physically, they are observed to flow like liquids showing some properties of
crystalline solids. Hence this state is considered to be the next state of matter known
as liquid crystal (LC) state.
• The LC state is also known as mesophase and can be defined as the condensed
matter that exhibit intermediate thermodynamic phase between the crystalline solid
and simple liquid state.
• In 1888, Austrian Botanical physiologist Friedrich Reintzer, examined the physico-
chemical properties of various derivatives of cholesterol which now belong to the
class of materials known as cholesteric crystals.
• At 145 °C, it melts into a cloudy liquid, and at 178.5 °C it melts again and the cloudy
liquid become clear. The phenomena is reversible.

Phenomena:
As temperature increases, First liquid crystal phase is smectic A, where there is a layer like
arrangement as well as translational and rotational motion of the molecules.
Further increase in temperature leads to nematic phase where molecules rapidly diffuse
out of the initial lattice structure and from layer like arrangement as well.
At highest temperature, the material becomes an isotropic liquid where the motion of the
molecules changes yet again.
 • The amount of energy required to cause the phase transition is called latent heat of
the transition and is useful to measure of how different two phases are.
• In case of cholesteryl myristate, the latent heat of solid to liquid crystal is 65
calories/gram, while latent for crystal to liquid transition is 7 calories/gram.
• The smallness in latent heat of liquid crystal to liquid phase transition is evidence that
liquid crystal are more similar to liquids than they are to solid.

Figure: Diagrammatic Presentation Liquid Crystal

Glassy States
• Glass is a state of matter.
• Glasses combine some properties of crystals and some of liquids but are distinctly
different from both.
• Glasses have the mechanical rigidity of crystals, but the random disordered
arrangement of molecules that characterizes liquids.
• Glasses are usually formed by melting crystalline materials at very high temperatures.
• When the melt cools, the atoms are locked into a random (disordered) state before
they can form into a perfect crystal arrangement.
• Although glass is said to be solid state, it can neither be a considered as a typical solid
nor a typical liquid. The atoms and molecules in most solid most solids are arranged
in an orderly manner whereas in glassy materials these are highly disordered. Glassy
material also do not have a specific melting point but these slowly and gradually
liquify on heating,
• Structurally glassy materials can be considered to be made up of a random selection
of polyhedral molecules linked together at their corners. Certain materials can easily
be converted to a glassy state while other pose great difficulty and certain materials
cannot be converted at all. Although the theory behind this behavior is not very clear,
it has been shown that materials which can be converted to glassy state have a high
viscosity at their melting point which inhibits the formation of an ordered structure.
• Although the most common materials which can be converted to glassy state are the
metal oxides, material such as steel can be converted to the glassy state if it is cooled
very quickly. This technique produces glasses since the material solidifies even before
it gets a chance to develop a crystalline structure.