Chapter – 2

Thermal Properties
of
Materials

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 Unit Two contents
✓ Thermal properties of Materials (Metal, Ceramics,
Polymer)
✓ Theory of specific heat(Einstein’s Theory)
✓ Classical Theory of specific heat (Dulong- Petit Law)

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Thermal properties:- refers to material traits or
features that are affected by temperature or heat.
✓ It is the response produced by the material when subjected
to Thermal Energy (Heat).

Thermal Response

Change in Temperature-
✓ Thermal Capacity
Change in Dimensions
✓ Thermal Expansion
Transmission of Thermal Energy
✓ Thermal Conduction

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✓ Heat energy is the measure of the total internal energy of a
system. This includes the total kinetic energy of the system
and the potential energy of the molecules.
✓ The internal energy of a system can be changed by either
supplying heat energy to it, or doing work on it.
✓ The internal energy of a system is found to increase with
the increase in temperature. This increase in internal
energy depends on the temperature difference, the
amount of matter, etc.

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Heat is absorbed through different mechanisms: lattice
vibrations and electronic contribution.
✓ The existence of the periodic crystal lattice in solid
materials provides a medium for characteristic vibrations.
Between the lattice spacing, there are quantized
vibrational modes called a phonon which is special type
of vibrational motion.
✓ lattice vibration:- Constituent atoms in a crystal vibrate
around their equilibrium positions due to thermal
energy. "Lattice vibration" means that atoms vibrate each
other with a specific phase relationship.

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 Heat/thermal Capacity
Heat capacity is a property that indicates the ability of a
material to absorb heat and change its temperature, thus
measuring the external energy required to increase a unit of
temperature of given quantity of matter (typically by 1°C or 1°C).
✓ Heat capacity is an extensive property:- It depends on its
size or quantity of matter.
Mathematically, it is expressed as: heat capacity (C) is equal to
the rate of change of heat (Q) with respect to change of
temperature (T):

The SI unit for heat capacity of an object is joule per kelvin (J/K
or J⋅K−1)

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There are three types of heat capacity namely,
✓Molar Heat Capacity (C),
✓Specific Heat Capacity,
✓Cp and Cv.
Specific Heat Capacity:- is defined as the amount of heat
absorbed or rejected by the unit mass of the substance
(undergoing no physical change) to change its temperature
by one unit.
Specific heat capacity is the intensive property as it is
independent of the quantity or size of the matter. It
depends on the nature of the substance and its
temperature.

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✓ Mathematically, it is expressed as:-
Q = C m ∆T
Where
C = Specific heat capacity of a substance depends on the
nature of the material of the substance. S.I unit of specific
heat is J kg-1 K-1.
Q= heat energy
m= mass and ∆T= change in temperature

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 Molar Heat Capacity (C):-Molar heat capacity is defined
as the amount of heat required to raise 1 mole of a
substance by 1 degree Kelvin.
✓ Molar heat capacity is very similar to specific heat
capacity but measures per mole instead of per gram of
substance.
Specific heat in constant volume(Cv) is the amount of heat
energy that a substance absorbs or releases with the
change in temperature where a volume change does not
occur.
Specific Heat in constant pressure(Cp) is the amount of
heat energy that a substance absorbs or releases with the
change in temperature where a pressure change does not
occur.

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Heat capacity at constant pressure, Cp, is always higher than
heat capacity at constant volume, Cv.

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 Classical Theory of specific heat
(Dulong- Petit Law)
The Dulong petit rules states that the product of specific
heat capacity and the molar mass of any element in its
solid state is a constant.

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 This graph clearly shows that the law is applicable at
various higher temperatures for different elements

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Limitations of Dulong Petit Law
✓ The Dulong Petit law is only relevant to the heavier
elements.
✓ It is only applicable to elements that are in solid form.
✓ It cannot be applied to lighter elements having high
melting points.
✓ It only gives a rough atomic mass.

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 Quantum Theory of specific heat
(Einstein’s Theory)
The Einstein theory of specific heat is a quantum
mechanical model proposed by Albert Einstein to explain
the behavior of specific heat in solids. According to this
theory, the atoms in a solid can vibrate at different
frequencies, and each frequency is associated with a
quantum of energy.
In Einstein's theory, the crystal lattice structure of a solid
comprising N atoms can be treated as an assembly of 3N
distinguishable one-dimensional oscillators. This
assumption is based on that each atom is free to move in
three dimensions.

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✓ When the temperature of the solid is increased, the atoms
are set into simple harmonic vibrations about their mean
positions with a frequency v, which is characteristic of a
solid and is called Einstein's frequency.
Einstein (1907): model a solid as a collection of 3N independ
ent 1-D oscillators, all with constant , and use Planck’s equ
ation for energy levels.
[later QM showed En = (n + 12 )  is actually correct]

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This was the same conclusion that was drawn about
blackbody radiation. The statistical distribution of energy in
the vibrational states gives average energy.

For high temperatures, this expression approaches agree

ment with the Law of Dulong and Petit.

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Einstein's derivation of specific heat formula is based upon
the following assumptions:

✓ Crystalline solid with N atoms can be considered as 3N h

armonic oscillator which vibrate independently with the
same frequency v.
✓ This oscillators are quantum oscillator
✓ The vibration of oscillator obeys Maxwell Boltzmann stat
istics

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 Debye’s Theory of specific heat

Theory in wave mechanics: the energy of thermal agitation in

a crystal is distributed among the possible systems of
standing waves that correspond to the normal modes of
elastic vibration.
✓ Einstein's oscillator treatment of specific heat gave qualita
tive agreement with experiment and gave the correct high
temperature limit (the Law of Dulong and Petit).

✓ The quantitative fit to experiment was improved by Deby

e's recognition that there was a maximum number of m
odes of vibration in a solid.

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✓ He pictured the vibrations as standing wave modes in the
crystal, similar to the electromagnetic modes in a cavity w
hich successfully explained blackbody radiation.
✓ The density of states for these modes, which are called "p
honons", is of the same form as the photon density of
states in a cavity.
Debye treated the solid as a continuous elastic body in which
the vibrations of the atoms generate stationary waves. Accor
ding to Debye, the atoms in a solid do not vibrate independe
ntly with same frequency.
✓ The Debye model assumes that atoms in materials move i
n a collective fashion.

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To impose a finite limit on the number of modes in the
solid, Debye used a maximum allowed phonon
frequency now called the Debye frequency uD. In the
treatment of specific heat, we define a Debye temperature
by

For low temperatures, Debye's treatment led to a specific heat

The dependence upon the cube of the temperature

agreed with experimental results for nonmetals, and for
metals when the electron specific heat was taken into
account
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 Debye’s Theory of specific heat

Heat capacity has a weak temperature depend

ence at high temperatures (above Debye temp
erature θD) but decreases down to zero as T a
pproaches 0K.
✓ The low-T behavior can be explained by
quantum theory.
✓ The first explanation was proposed by Eins
tein in 1906. He considered a solid as an e
nsemble of independent quantum harmon
ic oscillators vibrating at a frequency ν.
✓ Debye advanced the theory by treating th
e quantum oscillators as collective modes i
n the solid (phonons) and showed that

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 ✓ At low temperatures, vibrational heat contribution of hea
t capacity varies with temperature as follows:

✓ The above relation is not valid above a specific temperat

ure known as Debye temperature. The saturation value is
approximately equal to 3R.

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 Applications of Specific Heat
✓ Substances having a small specific heat capacity can be qui
ckly heated up, it also experience a big change in temper
ature even though only small amount of heat is supplied.
✓ Substances having a small specific heat capacity, are very us
eful as material in cooking instruments such as frying pans,
pots, kettles and so on, because, they can be quickly heated
up even when small amount oh heat is supplied.
✓ Substances that have a high specific heat capacity is suitabl
e as a material for constructing kettle handlers, insulators a
nd oven covers, because, a high amount of heat will cause
only a small change in temperature aka the material won't
get hot too fast

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✓ Sensitive thermometers also must be made from materials
with small specific heat capacity so that it can detect and s
how a change of temperature rapidly and accurately.

✓ Heat storage instruments are very useful and they are usua
lly made of substances with a high specific heat capacity.
✓ Water as a cooling agent acts excellent as a cooling agent i
n engines. Water is also used in houses in cold climate cou
ntries because as it is heated up (boiled) it tends to retain
heat and warm the house due to its high specific heat cap
acity

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Characteristics of an object with low specific heat:
✓ Fast heated up: have a faster temperature increase
✓ Fast cooled down: have a faster temperature decrease
✓ Sensitive to temperature changes
- Ex: Aluminium, copper etc
- Frying pans, pots, kettles- Low Specific Heat.
Characteristics of an object with high specific heat:
✓ Heats up and cools down at a slower rate
✓ Requires more heat to rise its temperature by a specific
amount
✓ Can absorb a great amount of heat
-Ex: plastic, water, concrete etc.
-kettle handlers, insulators and oven covers- high specifi
c heat capacity

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 Thermal Expansion
Thermal expansion is the tendency of materials to change in
size or volume after changes in temperature.
✓ Thermal expansion occurs because heated molecules move
faster and take up more space.
✓ When an object is heated or cooled, its length changes by an
amount proportional to the original length and the change
in temperature. Which is called linear expansion.

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ΔL = αLΔT is the formula for linear thermal expansion,
where ΔL is the change in length L,
ΔT is the change in temperature, and
α is the linear expansion coefficient, which varies slightly
with temperature.
✓ The coefficient of linear thermal expansion (CLTE) describes
the length change of a material as a function of the
temperature.
α values: for metals 5-25x10-6 , for ceramics 0.5-15x10-6 ,for
polymers 50-400x10-6
An instrument known as dilatometer is used to measure
the thermal expansion coefficient.

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When a solid is in bulk form that is in the form of a cube, or
sphere, etc. then on heating, its volume increases, this is
called volume expansion.
✓ It is observed that if the change in volume of the solid
is ∆V then ∆V proportional to the product of the original
volume(V) and the change in temperature(∆T).
ΔV = Vo β ΔT,
The coefficient of volume expansion (β)of the material of
bulk solid is defined as the increase in its volume per unit of
original volume per degree rise in temperature

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 Volume
expansion

Area Expansion is the growth of an object's surface, or

stretching its area alone. An area expansion is a two-
dimensional material expansion.
On heating, if the length and breadth of the object get
changed, it is called area expansion.
The area thermal expansion coefficient relates the change
in a material's area dimensions to a change in temperature.
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 Area Expansion

What is the relationship between coefficient of linear,

volume and area expansion?

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Thermal Expansion in Metals:
✓ Linear coefficients of thermal expansion for some of the
common metals range between about (5 x 10-6 & 25 x 10-6 )
°C-1.
✓ Iron-nickel and iron-nickel-cobalt alloys that have αl values
on the order of (1 x 10-6 ) °C-1.
Thermal Expansion in Ceramics:
✓ Relatively strong inter-atomic bonding forces are found in
many ceramic materials
✓ Comparatively low coefficients of thermal expansion range
between about (0.5 x10-6 & 15 x 10-6) °C-1.
✓ For non-crystalline ceramics and also those having cubic
crystal structures, αl is isotropic otherwise it is anisotropic.
✓ For inorganic glasses, the coefficient of expansion is
dependent on composition.

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Thermal Expansion in Polymers
✓ polymeric materials experience very large thermal
expansions upon heating. coefficients that range from (50
x 10-6 to 400 x 10-6 ) °C-1.
✓ Expansion is higher in linear and branched polymers
because the secondary intermolecular bonds are weak and
minimum of cross linking.
✓ With increased cross linking expansion coefficient
diminishes; the lowest coefficients are found in the
thermosetting network polymers such as phenol-
formaldehyde, in which the bonding is almost entirely
covalent.

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 Changes in dimensions with temperature are due to
change in inter-atomic distance, rather than increase in
vibrational amplitude.

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 Application of thermal Expansions

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 Question
1. An aluminum bar has a length of 2 meter at a
temperature of 70 degree Fahrenheit. What is its length
when its temperature is 100 degree Fahrenheit.
coefficients of linear thermal expansion for aluminum is
22*10-6 per degree Celsius.

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 Thermal conductivity
Thermal conductivity refers to the ability of a given material
to conduct/transfer heat.

K = thermal conductivity
Q = amount of heat transferred
D = distance between the two isothermal
planes
A = area of the surface
∆T = difference in temperature
It has the SI units of W/m·K (Watts per meter
Kelvin
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Its value range
✓ for metals 20-400 W/m.K
✓ for ceramics 2-50 W/m.K
✓ for polymers order of 0.3 W/m.K

Mechanisms - Thermal conductivity

1) the migration of free electrons and
2) lattice vibrations (phonons). The first mechanism dominat
es in pure metals and the second in non-metallic solids.
In metals, electronic contribution is very high. Thus metals ha
ve higher thermal conductivities. It is same as electrical cond
uction. Both conductivities are related through Wiedemann-F
ranz law:

where L – Lorentz constant (5.5x10-9 cal.ohm/sec.K2)

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With increase in temperature, both number of carrier electr
ons and contribution of lattice vibrations increase. Thus the
rmal conductivity of a metal is expected to increase.
k=kl+ke
Where kl and ke represent the lattice vibration and electron
thermal conductivities
✓ However, because of greater lattice vibrations, electron
mobility decreases.

Question
What happen to the electrical conductivity of metals and se
miconductors? When temperature is increases

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Thermal conductivity in Metals:
✓ Common metals values generally range between about 20
and 400 W/m-K.
✓ Here free electrons are responsible for both electrical and
thermal conduction in pure metal. Wiedemann–Franz law
✓ Alloying metals with impurities results in a reduction in the
thermal conductivity copper–zinc alloys- Plot
Thermal Conductivity in Ceramics:
✓ Nonmetallic materials are thermal insulators
✓ Amorphous ceramics have lower conductivities than
crystalline ceramics, since the phonon scattering is much
more effective when the atomic structure is highly
disordered and irregular

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Thermal Conductivity in Polymers:

✓ Thermal conductivities for most polymers are on the

order of 0.3 W/m-K

✓ Highly crystalline and ordered structure will have a

greater conductivity than the equivalent amorphous
material, due to the more effective coordinated vibration
of the molecular chains for the crystalline state..

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Applications of Thermal Conductivity:
• Observed in aluminum sheets used in houses to block the
incoming and outgoing of air to keep warmth inside.
• Materials like graphene and diamonds are used recently
to transfer heat.
• Elements like copper, steel can be used in electric circuits
for conductivity.
• Carbon nanotubes are found to have good thermal
conductivity. Hence they can be used as electrodes in
batteries and capacitors.

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 Question
A wooden watering trough 3.1cm thick with a cross-
sectional area of 2.2m2 is placed on the ground. The
ground has a temperature of 302k and the water in the
trough has a temperature of 288.7K. If the heat transfer is
initially found to be 188.7 joule per second. What is the
thermal conductivity of the wood.

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