Thermal Physics

Kinetic theory of solids, liquids

and gases
This theory is based on the three experimentally
confirmed results:

the matter of any state is made of the particles,

tiny entities – atoms, which are typically 10 -10 m in
diameter; molecules, ions; there is a discrete
structure of a matter, since there is an empty space
between the particles
these particles in a
matter move;
they perform
permanent,
random, chaotic,
erratic, disordered
motion. The speed
of these particles
varies in any
direction and for
each particle, it is
also known as
thermal motion
the particles act to each other with attractive and
repulsive force; the magnitude of these forces depends
on the distance between the particles. The evidence for
these forces is a definite shape of solid matter objects,
a request of external force to change the volume of
solid matter, liquids and gases, interaction during the
collision
If the distance between the particles is R the force
between the particles is zero – the particles are in
equilibrium.
Example:
NaCl (R = 0.281 nm), H2 (R = 0.074 nm)
If the distance between the two particles is less
than R, the repulsive force becomes the dominant
one and increases rapidly.

If the distance between the two particles is greater

than R, the attractive force becomes the dominant
but only to a certain distance. If the distance keeps
on increasing the attractive force decreases rapidly
to zero.

That is why the particle is under the influence of

the nearest particles only.
The diffusion, Brownian motion, the pressure in
gases and other experiments are the evidence for
the permanent and disordered motion.
 The structure of the matter

The distinction between solids, liquids and gases

can be attributed to the strength of the attractive
forces between the atoms or molecules and to
their average speed.
 The solid state
the matter, usually, has a regular structure, the
particles are ordered in a certain way and strictly
bound to each other in a crystal lattice. If the
regular structure disappears at the distance of
several ponds, we call these solids to be
amorphous; these substance does not possess a
long – range order of atoms.
the average distance between the particles is 0.2
nm – 0.3 nm

the solids are rigid, have fixed volume and fixed

shape, however the particles can vibrate within a
limited area

the net potential energy of particles is greater than

the net kinetic energy of the vibrational motion of
particles
 The liquid state
the particles can move more freely than the
particles of solids

they can flow easily around one another

they are kept from flying apart by attractive forces

between them

they are not rigid

they do not have fixed shape; they assume the shape
of their containers

they have fixed volume

the average distance between two particles is

approximately 0.2 nm

the particles are ordered only for a very short time;

they can vibrate about the equilibrium position but
this position changes in time
the net potential energy (the instant position to the
equilibrium position) of particles is comparable to
the net kinetic energy of the particles
 The gas
the particles fly in all directions at great speeds of
different values

they are so far apart that the attractive forces

between them can be neglected

the distances between the particles are much

greater than the size of the particle - molecule
they are not rigid

they do not have a fixed volume

they do not have a fixed shape

the change of the velocity (its direction and

magnitude) takes place during the collisions
between the particles
the duration of the collision is much less than the
time between two collisions

it is assumed, the particles perform uniform straight

line motion between the collisions

the net potential energy of particles is much less

than the net kinetic energy of the particles
 The plasma
it is a mixture of electrically charged particles;
electrons and nuclei; and neutral particles

this can happen at very high temperatures – stars,

electric spark, lightning
 Temperature and absolute
temperature
The temperature is a measure of how hot or cold
something is.

Many properties of matter changes with

temperature; the length, volume, electrical
resistance, magnetic properties, pressure, etc.

The instruments designed to measure temperature

are called thermometers.
The operation of the thermometer depends always on a
property of a matter that changes with temperature.

The first idea for a thermometer, by Galileo, used the

expansion of a gas.
Today, a hollow glass tube filled with mercury or
alcohol coloured with a dye – thermal expansion
of a liquid.

The clinical thermometer uses the change of the

density with temperature.
The change of the length of a metallic strip
with temperature – bimetallic thermometer.
The change of electrical properties and radiation –
a digital thermometer, contactless thermometer
(non contact thermometer)
 Temperature scales
There are three temperature scales generally used:

The Fahrenheit scale

The Celsius scale

The Kelvin or absolute scale

Daniel Gabriel Fahrenheit
(1686–1736)
Dutch – German – Polish physicist,
inventor and scientific instrument
maker in 1724, invented a modern
mercury – in – glass thermometer

The Fahrenheit scale is defined by

two points: the freezing point of
water (a temperature at which
water freezes into ice) as 32 °F and
the boiling point of water as 212
°F. This scale is divided into 180
°F segments, at a sea level and
standard atmospheric pressure.
Anders Celsius
(1701 – 1744) Swedish
astronomer, physicist and
mathematician

He has founded Uppsala

Astronomical Observatory
in 1741 and in 1742 the
centigrade scale, which has
been renamed to his honour
Celsius scale
William Thomson, 1st
Baron Kelvin (1824 –
1907)
Scots – Irish
mathematical physicist
and engeneer
At the University of
Glasgow he did
important work in the
mathematical analysis of
electricity and
formulation of the first
and second laws of
thermodynamics.
He also had a career as an electric telegraph
engineer and inventor. For his work on the
transatlantic telegraph project he was knighted in
1866 by Queen Victoria, becoming Sir William
Thomson. He had extensive maritime interests and
was most noted for his work on the mariner’s
compass, which had previously been limited in
reliability.
The Kelvin scale has one fundamental
temperature, it is a temperature of an
equilibrium state of a system
ICE – WATER – STEAM
It is a triple point of water, T = 273, 16 K
= 0.01 °C.
The temperature of 0 K is a beginning of a
thermodynamic scale, there is not any
negative value of temperature in the
thermodynamic scale.
The conversion between the Celsius and
Kelvin scale

t = (T – 273.15) °C
T = (t + 273.15) K
 A “scientific” note
n – an amount of substance, unit is one
mole; [n] = mol N
n
N – number of particles NA
NA – Avogadro’s number = number of
particles in one mole
m
6.022x10 mol
23 -1
n
Mm
m – mass of a sample
Mm – molar mass = a mass of one mole
Atomic mass unit; mu = u =1/12 of mass of
a carbon (12C) = 1.6605x10-27 kg

Relative atomic mass; Ar; expresses how

many times is a mass of an atom greater
than u

Relative molecular mass; Mr; expresses

how many times is a mass of a molecule
greater than u
Mass of an atom
m = Ar x u; [m] = kg

Mass of a molecule
m = Mr x u; [m] = kg
Mr = sum of Ar of all atoms in a molecule

Molar mass = mass of one mole

Mm = Ar g.mol-1 = Ar x 10-3 kg.mol-1
Mm = Mr g.mol-1 = Mr x 10-3 kg.mol-1
 Example
Nitrogen, atomic number 7, Ar = 14.0067

mass of atom = 14.0067u = 2.33 x 10-26 kg

mass of a molecule N2 = 2xAr = 28.0134u =

4.65 x 10-26 kg

molar mass of N2 = 28.0134 g.mol-1 =

28.0134 x 10-3 kg.mol-1
 Internal energy
The internal energy, U, equals the sum of the
kinetic energies of all particles and their potential
energies.

The internal energy can change by doing a work,

by a heat exchange or both.

When doing a work, the kinetic or the potential

energy of an object transforms into the internal
energy of an object.
U W
In an isolated system, the sum of the
kinetic, potential and internal energy of an
object remains constant.
U Q
During the heat exchange, the particles of a
warmer object collide with the particles of a
colder object and the part of the energy of
these particles is transferred into the energy
of the particles of the colder object. The
heat exchange can happen by means of
radiation.
U W  Q
 The heat exchange
The heat Q is determined by the energy
transferred during the heat exchange from
the warmer object to the colder object.

The unit of the heat is Joule. [Q] = J

The heat capacity, C, of an object is
defined as the amount of heat divided by
the temperature change.

It determines, how much heat can an object

receive or release to undergo the
temperature change by ΔT.

Q
C
T
The specific heat capacity, c, is defined as the
heat capacity of an object divided by the mass of
an object.

It is equal to the heat which one kilogram of a

certain matter can receive or release during the
heat exchange

C Q
c  Q mcT
m m T
 heat released = heat gained

The energy is conserved during the heat

exchange, if the system is isolated.

Q1 Q2
m1c1T1 m2 c2 T2
 The Latent Heat
When the state or a phase changes, the energy is
supplied or released.

The energy supplied or released during the phase

change is called the latent heat.

This heat is used to change the bonds between the

particles – to overcome the potential energy
associated with the forces between the molecules.
The work must be done against these
attractive forces to free the molecules from
their relatively fixed positions in the solid,
so they can freely roll over one another in
the liquid phase. Similarly, from liquid
phase to gaseous phase. This process is a
more violent reorganization of the
molecules than is melting, therefore the heat
of vaporization is generally much greater
than the heat of fusion for a given
substance.
It is not used to rise the temperature of a
matter, to rise the average kinetic energy of
particles.
Lf – the latent heat of fusion
L f l f m
Lv – the latent heat of
vaporisation

lf – the specific latent heat of Lv lv m

fusion
lv – the specific latent heat
of vaporisation
melting – freezing
evaporation – condensation
sublimation – desublimation

The heat transfer – conduction, convection, radiation

 Conduction
In many materials, the heat conduction is carried
out via molecular collisions.

As one end of an object is heated, the molecules

there move faster – they gain energy from a heater
or warmer object.

As they collide with their slower-moving

neighbors, they transfer some of their kinetic
energy to these molecules.
Their speeds increase, their kinetic energies
increase, as well.

This happens along the whole object,

farther and farther – the kinetic energy of
thermal motion is transferred by molecular
collisions along the object.

Heat conduction from one point to another

takes place only if there is a difference in
temperatures between the two points.
 Convection
Convection takes place in liquids and gases,
which are not very good conductors of heat.
Although liquids and gases are not very
good heat conductors, they can transfer heat
quite rapidly by convection.
Convection is a process whereby heat flows
by the mass movement of molecules from
one place to another.
Convection involves motion of large numbers of
molecules over large distances.
The air above the heater
expands as it is heated, and
hence its density decreases.
Because its density is less
than that of the surrounding
cooler air, it rises.
The cold air moves down,
since it has higher density.
Example: warm and cold ocean currents, wind, weather in general
 Radiation
Convection and conduction require the
presence of matter as a medium to carry the
heat from the hotter to the colder region.
Radiation occurs without any medium at all.
We all depend on the energy radiated from
the Sun, through an empty space (or nearly
empty)
σ is the Stefan – Boltzmann constant, equal
to 5.67x10-8 Wm-2K-4
A good absorber is a good emitter.
Any object not only emits energy by
radiation but also absorbs energy radiated
by other bodies.
If an object surface temperature of an object
is T1 and the
 Postulates of Kinetic Theory
1. There are a large number of molecules, N,
each of mass m, moving in random
directions with a variety of speeds. This
assumption is in accord with our
observation that a gas fills its container and,
in the case of air on Earth, is kept from
escaping only by the force of gravity.
2. The molecules are, on the average, far apart
from one another. That is, their average
separation is much greater than the diameter
of each molecule.
3. The molecules are assumed to obey the
laws of classical mechanics, and are
assumed to interact with one another only
when they collide. Although molecules
exert weak attractive forces on each other
between collisions, the potential energy
associated with these forces is small
compared to the kinetic energy, and we
ignore it for now.
4. Collisions with another molecule or the
wall of the vessel are assumed to be
perfectly elastic. We assume the collisions
are of very short duration compared to the
time between collisions. Then we can
ignore the potential energy associated with
collisions in comparison to the kinetic
energy between collisions.