UNIT 3

PHYSICAL STATES OF MATTER

Introduction
• Matter is defined as anything occupying space and having mass,
which is the material of the Universe.
• It exists in three common states: gas, liquid and solid
• The three physical states of water are:
 Steam (water vapor): gaseous state of water
 Water: liquid state of water
 Ice: solid state of water

• Most solids change to liquids and most liquids change to gases as

they are heated.
• Liquids and gases are known as fluids because they flow freely.
• Solids and liquids are referred to as condensed states because
they have much higher densities than gases.
• Generally, the physical states of matter can be changed to solids,
liquids, gases, or plasma by varying temperature and/or pressure
 Solid
• A solid is rigid; it has a fixed volume and a fixed shape.
• Solids cannot be compressed.
• Solids have higher densities than liquids because their
particles are usually packed closer than those in liquids.
• The tightly packed particles of solids are also highly
organized.
• The particles of a solid, whether they are atoms, ions or
molecules, only vibrate at a fixed point with respect to
the neighboring particles.
• As a result, its particles stay in a fixed position.
• Metals, chalk, sand, soil, and stone are examples of
solids
 Liquid
• A liquid has a definite volume, but does not have a definite shape.
• It takes the shape of its container.
• It is very slightly compressible and has the ability to flow.
• In a liquid, particles vibrate about a point, and constantly shift their
positions.
• Water, ethanol, mercury, bromine, and oil are examples of liquids

Gas
• A gas has neither definite volume nor definite shape; it takes on the
shape and volume of its container.
• Gas is highly compressible because most of the volume of a gas is
composed of the large amounts of empty space between the gas
particles.
• For example, air, hydrogen, oxygen, carbon dioxide, and nitrogen are
gases
 Plasma
• Plasma is the fourth physical state of matter that exists at
a high temperature (million degrees Celsius).
• At such high temperatures molecules cannot exist.
• Most or all of the atoms are stripped of their electrons and
thus, exist in their ionized form.
• This state of matter, a gaseous mixture of positive ions
and electrons, is called plasma.
• In another word, plasma is an ionized gas. Because of the
extreme temperatures needed for fusion, no material can
exist in the plasma state.
• Like gases, plasmas have no fixed shape and a fixed
volume. They are also less dense than solids or liquids
kinetic theory and properties of matter
kinetic theory and properties of matter
• The three states of matter in which substances are
chemically the same but physically different are explained
by the kinetic theory of matter.
• The kinetic theory of matter gives an explanation on the
nature of the motion and the heat energy.
• According to the kinetic theory of matter, every substance
consists of a very large number of very small particles
called ions, atoms and molecules.
• The particles are in a state of continuous and random
motion with all possible velocities.
• The motion of the particles increases with a rise in
temperature.
Generally, the kinetic theory of matter is based on the following assumptions:

 All matter is composed of particles that are constantly moving.

 All particles have kinetic energy (movement energy) and potential energy. Molecules
in the solid phase have the least amount of energy, while gas particles have the
greatest amount of energy.
 The difference between the three states of matter is the energy contents they have
and the motion of the particles. A change in phase may occur when the energy of
the particles is changed.
 The temperature of a substance is a measure of the average kinetic energy of the
particles.
 There are spaces between particles of matter. The average amount of empty space
between molecules gets progressively larger as a sample of matter moves from the
solid to the liquid and gas phases.
 There are attractive forces between atoms/molecules, and these become stronger
as the particles move closer together. These attractive forces are called
intermolecular forces
 Gases exert pressure in all directions. Gases that are confined in a container exert
pressure on the walls of their container. This pressure is due to collisions between
gas molecules and the walls of the container.
 Gases easily flow and diffuse through one another. A gas moves freely and randomly
throughout a given space
 Properties of Liquids
• Liquids have the following properties:
• Liquids have a definite volume, but have no definite
shape. They assume the shapes of their container. Lack
of a definite shape for liquid substances arises from low
intermolecular forces of attraction between their particles
as compared to that of solids.
• Liquids have higher densities than gases. Their density is
a result of the close arrangement of liquid particles. Thus,
the particles are closer in liquid than in their gaseous
state. This accounts for the higher densities of liquids as
compared to gases
 Liquids are slightly compressible. The available free
space between particles in liquids is very little as a
result, liquids resist an applied external force
 Liquids are fluids. A fluid is a substance that can easily
flow. Most liquids naturally flow downwards due to
gravitational force. But, the fluidity of liquids is much
slower than gases
 Properties of Solids
Solids have the following properties:
 Solids have a definite shape and definite volume, due to
the presence of the strong force of attraction between the
particles in a solid.
 Solids generally have higher densities than gases and
liquids. The particles of solids are very close to each
other, and thus, there is almost no free space between
the particles of solids. This closeness of particles makes
solids to have more particles (mass) per unit volume.
 Solids are extremely difficult to compress because the
high interparticle forces of attraction between the
particles of solids are very strong due to a very short
distance between them.
 Solids are not fluids. Solids normally do not flow because
particles of solids are rigidly held in position by strong
forces that restrict them
 The Gaseous State
Assumptions of the kinetic molecular theory of gases:
A gas is a collection of particles (molecules) in constant,
straight-line motion.
Gas particles do not attract or repel each other, they do not
interact. The particles collide with each other and with the
surfaces around them, but they bounce back from these
collisions like pool balls.
There is a lot of space between gas particles compared with
the size of the particles themselves. In other word, the volume
of the particles is negligible compared to the total volume of the
gas.
The molecules are so far apart, the total volume of the
molecules is extremely small compared with the total volume of
the gas.
This assumption explains why gases are so easily compressed
and why they can mix so readily
The average kinetic energy of gas particles is proportional to the temperature
of the gas in kelvins.
This means that as the temperature increases, the particles move faster and
therefore have more energy. The mathematically expressed as:

Generally, the gaseous state is characterized by the following physical

properties:
 Gases are highly compressible.
 Gases exert pressure equally in all directions.
 Gases have much lower density than solids and liquids.
 The volume and the shape of gases are not fixed. These take the volume
and shape of the container.
 Gases mix evenly and completely.
 Simplicity of gases is due to the fact that the forces of interaction between
their molecules are negligible.
 GAS LAWS
• The gas laws are the result of various research conducted
for several centuries on the physical properties of gases.
• The first reliable measurement on the properties of gases
was made by Robert Boyle in 1662 (an Anglo-Irish
scientist).
• The observation of Boyle’s and other scientists led to the
development of the gas laws.
• The gas laws express mathematical relationships
between the volume, temperature , pressure, and quantity
of a gas.
• Pressure: The pressure exerted by a gas sample is
defined as the force per unit area that results from the
collisions of gas particles with surrounding surfaces.
 Pressure is one of the measurable properties of gases. Thus, the
pressure of a gas can be expressed in unit of atmosphere, Pascal,
torr, millimeter of mercury.
 The SI unit of pressure is Pascal (Pa).
Volume:

 Volume is the space occupied by a substance.

 The SI unit of volume is the cubic meter (m3).
 Volume is also expressed in cubic centimeter (cm3) and cubic
decimeter (dm3). Other common units of volume are milliliter (mL)
and liter (L).
Temperature:

 Temperature is the degree of hotness or coldness of a body. Three temperature

scales are commonly used.
 These are °F(degrees Fahrenheit), °C (degrees Celsius) and K(Kelvin).
 In calculations, the Kelvin scale is usually used.
 The three units are inter-converted by Equations 3.3 and 3.4:

Molar Volume and Standard Conditions:

 The conditions of a pressure of 1 atmosphere and a temperature of 0oC

(273K) are called standard temperature and pressure (STP) for gases.
 At STP the volume of one mole of any gas is 22.4 liters. This volume is
known as the molar volume of gases.
 Boyle’s Law
• The first quantitative experiments on gases were performed by
Robert Boyle(1662).
• His experiment helped to understand the relationship between
the volume and pressure of a fixed amount of a gas at constant
temperature.
• On the basis of his experiments, Robert Boyle concluded that,
at constant temperature, the pressure of a fixed amount of gas
varies inversely with its volume
He discovered that at constant temperature doubling the pressure on a sample of gas
reduces its volume by one-half, and tripling the gas pressure reduces its volume to one-
third of the original.
Generally, the volume of a gas decreases, as the pressure on the gas increases
Generally, Boyle’s law states that the volume of a fixed mass of gas is inversely
proportional to the pressure at a constant temperature.
Mathematically this is written as:
 Charles’ Law
• Scientists was Jacques Charles (a French physicist), who
was the first person to fill a balloon with hydrogen gas and
who made the first balloon flight.
• In 1787, Charles found that the volume of a gas at
constant pressure increases linearly with the temperature
of the gas
• For example, doubling the Kelvin temperature causes the
volume of a gas to double, and reducing the Kelvin
temperature by half causes the volume of a gas to
decrease by half.
• This relationship between Kelvin temperature and the
volume of a gas is known as Charles’ law.
Charles’ law states that the volume of a fixed mass of gas at constant pressure varies
directly with the Kelvin temperature.
 Gay Lussac’s Law
• Joseph Louis Gay-Lussac (a French scientist) studied
how the pressure and temperature of a fixed amount of
gas at constant volume are related.
• The relationship that he established is called Gay-
Lussac’s law or the pressure-temperature law.
• It states that at constant volume, pressure of a fixed
amount of a gas varies directly with the temperature.
•Mathematically
The Combined Gas Law
A sample of a gas can undergo simultaneous changes in temperature, pressure, and
volume.
In such cases, the three variables should be considered at the same time. The three
gas laws we have learned can be brought together into a single equation known as the
combined gas law
The combined gas law expresses the relationship between pressure, volume, and
temperature of a fixed amount of gas.
Mathematically:
Avogadro’s law
In 1811, Amedeo Avogadro (an Italian scientist) suggested that at the same
temperature and pressure, equal volumes of gases contain equal numbers of moles.
This observation is called Avogadro’s law, shown as:
This equation states that for a gas at constant temperature and pressure, the volume is
directly proportional to the number of moles (molecules) of gas.
In other words, equal numbers of molecules of different gases compared at the same
temperature and pressure occupy equal volumes
For two samples of gas at the same temperature and pressure, the relation between
volumes and numbers of moles can be represented as:

 The volume occupied by a mole of gas at STP, is called the standard molar
volume. It is nearly constant for all gases.
 The standard molar volume of an ideal gas is equal to 22.4 L per mole at STP.
 For an ideal gas: 1mol gas = 22.4 L gas
 The Ideal Gas Equation
 An ideal gas is a hypothetical gas that obeys the gas
laws. • Real gases only obey the ideal gas laws closely at
high temperature and low pressure.
 The ideal gas law is a combination of Boyle’s law,
Charles’ law and Avogadro’s law. Boyle’s law: V α P(at
constant T and n) Charles’ law: Vα T(at constant P and n)
Avogadro’s law: V α n(at constant P and T)
 This relationship indicates how the volume of gas
depends on pressure, temperature and number of moles.
Graham’s Law of Diffusion
We have discussed that the gas molecules are in constant, rapid, random
motion and occupy quickly throughout any container. This spreading of gas
molecules throughout the container is called diffusion.
 Thomas Graham (1805-869), a Scottish chemist, studied the rate of
diffusion of different gases.
 He found that gases having low densities diffuse faster than gases that
have higher densities.
 Based on his observations, in 1829, he postulated the relationship
between the density of a gas and its rate of diffusion, which is known as
Graham’s law of diffusion
 Graham’s law of diffusion states that, at constant temperature and pressure, the
rate of diffusion of a gas, r, is inversely proportional to the square root of its
density, d, or molar mass, M.
LIQUID STATE
 As in a gas, particles in a liquid are in constant motion.
 However, the particles in a liquid are closer together than those in a gas.
 The attractive forces between particles in a liquid are stronger than between
particles of a gas.
 This attraction between liquid particles is caused by the intermolecular forces of
attraction such as dipole dipole forces, London dispersion forces, and hydrogen
bonding.
 Liquids are more ordered than gases because of the stronger intermolecular forces
and the lower mobility of liquid particles
 Energy Change in Liquids
 The process by which a liquid changes to a gas is known
as vaporization or evaporation.
 Evaporation is the process by which molecules on the
surface of a liquid break away and go into the gas phase.
 Molecules on the surface of a liquid are held less tightly
than those in the interior, so the most energetic molecule
can break away into the gas
 Evaporation is explained in terms of the energy that the molecules on the
surface of the liquid have.
 In an open container, evaporation continues until all of the liquid enters
the gas (vapor) phase (Figure 3.8).
 Most of the molecules that escape into the vapor phase do not collide with
the surface of the liquid and return to the liquid phase.
 Instead, they will diffuse through the gas phase away from the container
and equilibrium cannot be established.
 Under these conditions, the liquid will continue to evaporate until it has
disappeared.
 However, liquids in a closed container behave differently.
 The volume of the liquid decreases for some time, and then, remains
unchanged. This is because in closed containers, the vapor cannot escape.
 As more molecules leave the liquid, more gaseous molecules collide with
the container walls, with each other, and with the liquid surface and
return to the original liquid state
 The process of when a vapor returns to the liquid state is called
condensation.
 Evaporation and condensation are opposing processes.
 Evaporation is a liquid turning into a gas, and condensation is a gas
turning into a liquid.
For instance, when liquid water is initially put into a closed container, more evaporation
happens than condensation because there are so few gaseous water molecules in the
space above the water (Figure 3.9a).
However, as the number of gaseous water molecules increases, the rate of
condensation also increases (Figure 3.9b).
At the point where the rates of condensation and evaporation become equal (Figure
3.9c),dynamic equilibrium is reached and the number of gaseous water molecules
above the liquid remains constant
The rate of evaporation of a liquid can be affected by these factors:
 Temperature
 Intermolecular forces
 Surface area of the liquid.

Temperature
 An increase in temperature increases the average kinetic energy of the
molecules and thus increases the tendency to change into the gaseous
state.
 Some liquids evaporate readily at room temperature. Such liquids are said
to be volatile.
 Volatile liquids have relatively weak forces of attraction between particles.
 Liquids such as formaldehyde, ethyl alcohol, mercury, and benzene are
volatile liquids.
Liquids that do not vaporize easily at a given temperature are said to be nonvolatile.
They have relatively stronger attractive forces between their molecules.
Liquids such as motor oil, edible oil, glycerin, water, and molten ionic compounds are
nonvolatile.
Vapor pressure
 The partial pressure of the vapor above a liquid is called vapor pressure.
 The vapor pressure of a liquid depends up on the temperature.
 At a given temperature, vapor pressure is constant.
 The vapor pressures of liquids always increase as temperature increases
because the rate of evaporation increases with increasing temperature.
Intermolecular forces
 Vapor pressure depends also on the intermolecular forces between the molecules of
the liquid.
 The stronger the intermolecular forces, the lower will be the vapor pressure of the
liquid because fewer molecules will have enough kinetic energy to overcome the
attractive force at a given temperature.
 For example, water and ethanol have relatively low vapor pressure because the very
strong hydrogen bonding in these liquids account for their unusually low vapor
pressures.
 However, liquids with low intermolecular forces have high vapor pressures at room
temperature.
 For example, diethyl ether, a non-polar molecule with relatively weak dispersion
forces, has a relatively higher vapor pressure.
 Surface area of the liquid
• Evaporation occurs at the liquids surface, where it interfaces
with the air surrounding it.
• Liquid surface area is the amount of liquid that is exposed to
the atmosphere (air).
• The number of liquid molecules present at the surface
increases as the surface area of the container (or the surface
area occupied by the liquid) increases.
• This, in turn, increases the number of molecules that separate
from the liquid surface and change into gases at a specific
moment, increasing the rate of evaporation.
• However, for liquids having the same surface area, the rate of
evaporation depends on the two factors: Temperature and The
strengths of intermolecular attractions.
 Boiling and Boiling Point
• When heat energy is added to a liquid, it increases the
kinetic energy of the molecules and the temperature of
the liquid increases.
• Heating a liquid always increases its vapor pressure.
• When a liquid is heated to a sufficiently high temperature
under a given applied (usually atmospheric) pressure,
bubbles of vapor begin to form below the surface.
• If the vapor pressure inside the bubbles is less than the
applied pressure on the surface of the liquid, the bubbles
collapse as soon as they form.
 On the other hand, if the temperature is raised sufficiently, the vapor
pressure is high enough that the bubbles can persist and rise to the surface,
and burst, releasing the vapor into the air.
 This process is called boiling. In short, boiling is the change of a liquid to
bubbles of vapor that appear throughout the liquids
 It is the conversion of liquid to vapor within the liquid as well as at its surface.
 During evaporation, only molecules at the surface escape into the vapor phase.
 It is the formation of vapor bubbles within the liquid itself that characterizes boiling
and distinguishes it from evaporation.
 If the temperature of the liquid is increased, the equilibrium vapor pressure also
increases.
 Finally, the boiling point is reached. The boiling point of a liquid is the temperature at
which its vapor pressure equals the external atmospheric pressure.
 The normal boiling point is the temperature at which the vapor pressure of a liquid is
equal to exactly one atmosphere
 For instance, water boils at 100 °C at 1.0 atmospheric pressure and thus, its normal
boiling point of water is 100 °C.
 Nevertheless, the boiling point of water at 0.83 atm is 95 °C. Generally, when the
pressure exerted on a liquid is varied, the boiling point of a liquid also varies
 Note that as heat energy is added to vaporize a pure liquid at its boiling
point, the temperature remains constant until the liquid is completely
changed to vapor .
 Then, the temperature begins to rise after the liquid is completely changed
to vapor.
 Boiling of a liquid requires a certain amount of heat energy to break the forces of
attraction between the molecules.
 The amount of heat energy necessary to bring about the vaporization of a fixed
amount of a liquid at a fixed temperature to the gaseous state is called the heat of
vaporization.
 The molar heat of vaporization is the amount of heat needed to convert 1 mole of a
liquid at its boiling point to a gas.
 It is equal to the amount of energy that is released when 1 mole of vapour
condenses to liquid at the condensing point of a vapour.
 During condensation heat is released.
 Thus, the amount of heat realized when 1 mole of a gas is converted to a liquid at
its condensation point is called the molar heat of condensation(∆Hcond).
 Molar heat of vaporization (∆Hvap) and molar heat of condensation (∆Hcond) are
equal in magnitude but opposite in sign:
Note that vaporization is an endothermic process whereas condensation is an
exothermic process.
SOLID STATE
 The temperature at which a pure liquid changes to a crystalline solid, or freezes, is
called the freezing point;
 it is identical to the melting point.
 The melting or freezing occurs at the temperature where the liquid and solid are in
dynamic equilibrium
 When a solid is continuously heated the ordered crystalline structure of solids will
be disturbed.
 As a result, particles gradually get freedom of motion and melting (or fusion) take
place.
 Melting is the process of converting solid into the liquid.
 The temperature at which a crystalline solid changes to a liquid or melts is called
the melting point
 On the other hand, when a liquid is cooled, its molecules come closer to one
another and thus, the intermolecular forces of attraction between them get stronger.
 As a result, its particles arrange themselves into a regular pattern and then
converted to a solid.
 This process is called freezing or solidification.
 For instance, ice melts at 0 °C and water freezes at 0 °C.
 Ice and water coexist in equilibrium at 0 °C as follows:
 Unlike boiling points, melting points are affected only by large pressure
changes. Note that both the melting point and the boiling point are
characteristics of physical properties of a substance and can be used to
help identify it. The amount of heat needed to convert one gram of solid
to liquid at the melting point is called heat of fusion.
 The molar heat of fusion or molar enthalpy of fusion (∆Hfus) is the
quantity of heat needed to convert one mole of a solid at its melting point
to the liquid state.
 Melting requires the supply of energy; therefore, it is an endothermic
process. During the process of solidification, the amount of heat
liberated is exactly equal to the heat of fusion.
 The heat liberated is called the heat of solidification or heat of
crystallization.
The molar heat of crystallization (∆Hcryst ) is the quantity of energy that is removed
from one mole of a liquid to convert it to the solid state at its freezing point

 Some solids have significant vapor pressure and thus, evaporate directly from
the solid to the vapor state without passing through the liquid state.
 This process is called sublimation,i.e., the change of solid to vapor.
 The opposite of sublimation is deposition that is the change of vapor to solid
 The enthalpy of sublimation, ΔHsub, is the energy required to convert one
mole of a substance from the solid to the gaseous state.
 Sublimation is an endothermic process.
 The enthalpy of deposition, ΔHdep, is the energy released when one mole
of a substance from the gaseous state change to solid.
The heat (enthalpy) of sublimation is related to the enthalpies of fusion
and vaporization by:

Heating curve
 Heating curve is a plot of the temperature versus the amount of heat
added
 It is commonly used to show the relationship between phase changes and
enthalpy for a given substance.
 There are two main observations that we can learn from the heating curve:
regions where the temperature increases as heat is added and plateaus
where the temperature stays constant.
 It is at plateaus that a phase change occurs
 UNIT 4
CHEMICAL KINETICS
Introduction
• Every chemical reaction proceeds at a different rate or
speed.
• Some reactions proceed very slowly and may take a
number of days to complete; while others are very rapid,
requiring only a few seconds.
• For example, rusting of iron could start quickly, while
ripening of fruits may be completed in a few days. On the
other hand, weathering of stone may take more than a
decade and the breakdown of plastics in the environment
takes more than hundred years.
• However, other reactions, like the combustion of gasoline
or the explosion of gunpowder occur in a few seconds.
 To beuseful reactions must occur at a reasonable rate.
 The area of chemistry that is concerned with reaction rates is called chemical
kinetics.
 The word “kinetic” suggests movement or change.
 Chemical kinetics refers to the rate of reaction, which is the change over times in
the concentration of a reactant or a product.
 The Rate of reaction
 The rate of a chemical reaction measures the change in concentration of a
reactant or a product per unit time.
 This means that the rate of a reaction determines how fast the concentration of a
reactant or product changes with time.
 For example, for a general reaction: Reactants →Products
 This equation tells us that, during the course of a reaction, reactant molecules are
consumed while product molecules are formed.
 As a result, we can follow the progress of a reaction by monitoring either the
decrease in concentration of the reactants or the increase in concentration of the
products
 It is more convenient to express the rate in terms of change in concentration with
time.
 Consider the progress of a simple reaction in which A molecules are converted to
B molecules: A →B

 in which, ∆[A] and ∆[B] are the changes in concentration (molL−1) over a period
∆t.
 Because the concentration of A decreases during the time interval, ∆[A] is a
negative quantity.
 The rate of a reaction is a positive quantity, so a minus sign is needed in the rate
expression to make the rate positive.
 On the other hand, the rate of product formation does not require a minus sign
because ∆[B] is a positive quantity (the concentration of B increases with time)
 For more complex reactions, we must be careful in writing the rate expression.
Consider, for example, the reaction: 2A →B
 Two moles of A disappear for each mole of B that forms, that is, the rate at which B
forms is one half the rate at which A disappears.
 We write the rate as either