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Topic 13: Thermal Properties of Materials

Melting and boiling at constant temperature:

The amount of heat supplied to change the state of a substance at constant temperature is known as latent heat.
Latent heat of fusion is the heat supplied during melting or the heat absorbed during solidification. Latent heat of
vaporization is the heat supplied during boiling or the heat absorbed during condensation.

Latent heat of vaporization of water and latent heat of fusion of water:

The molecules of solids vibrate to and fro alternately attracting and repelling one another. Their total energy can be
consist of two parts,

a. Kinetic energy which depends on the temperature, and 

b. Potential energy which depends on the force between the molecules and their distance apart.

During melting, liquids become solids at constant temperature. The molecules’ potential energy is therefore increased
and the additional energy required is the latent heat of fusion.
 When vaporization occurs the vapour occupies a much larger volume than the liquid so that energy is required to
separate the molecules against their mutual attractions (internal work )and extra energy is required to enable the
vapour to expand against the atmospheric pressure (external work). The total amount of heat supplied is the latent
heat of vaporization. That is why latent heat of vaporization is greater than the latent heat of fusion

Cooling and evaporation:

During evaporation molecules near the surface, which happen to be moving faster than average, can escape from the
attraction of their neighbours and come out of the liquid. In this way the liquid loses its most energetic molecules
while the less energetic ones are left behind. The average kinetic energy of the remaining molecules is therefore
reduced and this results in a fall in temperature.

specific heat capacity:


Symbol: c
Unit: J/kg K or J/ Kg 0 C
Definition: It is the amount of heat required to raise the temperature of 1 Kg of a substance by 1 K or 1 0 C.
Formula: H = m c Δθ

Determination of specific heat capacity

(a) Solids (good thermal conductors): A cylindrical block of the material is used, having holes for an electric heater (12 V,
2-4 A) and a thermometer. The mass m of the block is found and its initial temperature θ1 recorded. The block is lagged
with expanded polystyrene and a suitable steady current switched on as a stopwatch is started. The voltmeter and
ammeter readings V and I are noted. When the temperature has risen by about 10 K, the current is stopped and the time t
is noted for which it passed. The highest reading θ 2 on the thermometer is noted. Assuming that no energy loss occurs we
have:

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electrical energy supplied by heater = heat received by block

where c is the specific heat capacity of the metal. Hence

( b ) Liquids. The procedure is similar to that for solids except that the liquid is stirred continuously during the heating.
Assuming no heat loss:

energy supplied energy received energy received


by heater = by liquid + by calorimeter
and stirrer

lagging

specific latent heat of fusion:


Symbol: lf
Unit: J/kg or J/g
Definition: It is the amount of heat required to change 1 Kg of a substance from solid to liquid at constant temperature.
Formula: H = m lf

Determination of specific latent heat of fusion

The specific latent heat of fusion of ice can be determined by the method of mixtures. A calorimeter of mass, mc is two-
thirds filled with a mass mw of water warmed to about 5°C above room temperature. The temperature θ1, of the water is
noted, then a sufficient number of small pieces of dried ice at 0 oC, carefully dried in blotting paper, are added one at a
time and the mixture stirred, until the temperature is about 5 °C below room temperature The lowest temperature θ2 is
noted. The calorimeter and contents are then weighed to find the mass of ice m added. Assuming no heat loss:
heat given out by calorimeter heat used to melt ice heat used to warm melted ice
and water in cooling = at 0 °C + from 0 °C to θ2

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If cc and cw are the specific heat capacities of the calorimeter + stirrer and water respectively and lf is the specific latent
heat of fusion of ice then

mlf +

m(lf

lf

lf

specific latent heat of vaporisation:


Symbol: lv
Unit: J/kg or J/g
Definition: It is the amount of heat required to change 1 Kg of a substance from liquid to gas at constant temperature.
Formula: H = m lv

Determination of specific latent heat of vaporisation


A value can be found for lv by a continuous-flow-type method using the
apparatus shown. The liquid is heated electrically by a coil carrying a
steady current I and having a p.d. V across it. Vapour passes down the
inner tube of a condenser where it is changed back to liquid by cold
water flowing through the outer tube.
After the liquid has been boiling for some time it becomes surrounded
by a 'jacket' of vapour at its boiling-point and a steady state is reached
when the rate of vaporization equals the rate of condensation. If a mass
m of liquid is now collected in time t from the condenser, we have
l 1 t V1 = m1 lv + h ………..(1)
where lv is the specific latent heat of vaporization of the liquid and h is
the heat lost from the 'jacket' in time t. The 'jacket' of vapour makes h
small and if it is neglected lv can be found. Alternatively it may be
eliminated by a second determination with a different power input.,
then
l 2 t V2 = m2 lv + h ………..(2)

(2) – (1) : lv = ( l2 V2 - l1 t V1) t / ( m2 – m1 )

Concept of Thermal/Heat energy


Heat is a form of energy that raises the temperature of a substance. The temperature rise depends on the amount of heat
that the substance has gained. When temperature rises, each molecule of the substance absorbs and stores part of the
heat energy being supplied. Thus, the quantity of heat gained and stored by the substance depends on the following:

 The number of molecules in the substance, hence on the mass, m of the substance.
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 The temperature rise, Δθ of the substance.
 The nature of the substance, i.e. the specific heat capacity, c of the substance.

Internal Energy, U

The internal energy is the sum of kinetic and potential energy of the particles in a body.

U = E K + EP Δ EP = 0 for constant volume; EK is temperature dependent.

1. U Gas >U Liquid >U Solid

2. An object can be given more internal energy by:

 Supplying heat to it.


 Doing work on it (by compressing it)
3. A rise in temperature of a body corresponds to an increase in the Ek component hence U increases.
4. A change in state of a body at constant temperature corresponds to an increase in the EP component hence U
increases.

The 1st Law of Thermodynamics:

The 1st Law of Thermodynamics states that the total energy in a closed system is constant.

A system is the object or group of object that is being considered. This law follows from the Principle of Conservation of
Energy.
In equation form, Increase in Internal Energy = Heat transferred TO the system + Work done ON the system
In symbols,
∆U = q + W

Sign Convention:

Positive ( +q) if heat is supplied to the system


q
Negative ( -q) if heat is removed from the system

Positive ( +w) if work is done on the system


W
Negative ( -w) if work is done by the system

Positive if the system gains internal energy


∆U
Negative if the system loses internal energy

Ex.1. State and explain what happens to ∆U, q and W, if any when

(a) ice at 0 0C melts to become water at 0 0C. (Ep comp. increase; ∆U = +; q = + ; W = 0 or + (water contracts))
(b) the temperature of a gas increases from 20 0C to 50 0C at constant volume. (Ek comp. increase; ∆U = +; q = + ; W = 0
(no change in volume))

2. 200 J of heat is added to a system which does 150 J of work. Find ∆U. (q = +200 J; W = -150 J, so ∆U = 50 J)
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3. Explain why in an isothermal change, ∆U = 0. In such a change, 200 J of heat is added to a s system. State how
much work is done on or by the system? (no change in temp., so ∆U = 0; q = + 200 J; W = -ve ; ∆U = 200 –W ;
- W = - 200 J => W = 200 J; system does work)

Work done by a gas:

When a gas expands it does work on its surroundings. That work is equal to the area under the curve on a P-V diagram
which describes that expansion.
Suppose the piston is pushed upwards a distance x by the gas.

The pressure p pushing down on the piston exerts a force F = p A

To force the piston back a distance x against a force F = p A, an amount of work


equal to W = F x = p A x must be done by the gas. A x is the increase in volume
ΔV of the gas so we can write W = p ΔV.

p- V graphs:

1. Isochoric process (constant volume):


p
T2 > T1
1. Pressure increases from p1 to p2, showing that all the heat
p2
entering the system becomes internal energy. ΔU = q + W
T2 => ΔU = q + 0 => ΔU = q.
2. Temperature increases from T2 to T1.
p1 T1 pV
3. T = at any point.
nR
V

2. Isobaric process (constant pressure):

p
T2 > T1
1. Pressure remains constant but temp. increases from T2 to T1.
2. ΔU increases as temp. increases.
p T2 3. Work is done by system, W is negative.
4. ΔU = q – W
T1 5. W = p ΔV = area under graph.

V1 V2 V

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3. Isothermal process (constant temperature; very slow expansion):

p
1. As temp. remains constant, ΔU = 0
T2 > T1
2. Work is done by the system at the same rate as heat is supplied to it
v2
1
3. W = q = area under graph = n R T ∫ dv
p1 T2 v1
v

p2 T1
v2
=> W = n R T ln ( )
V1 V2 V v1

4. Adiabatic process:

p
1.No heat enters or leaves the system (very rapid expansion or compression.
T2 > T1
2. q = 0 => ΔU = - W (system does work)
p1
3. All the work is done at the expense of the internal energy so the gas cools.
T2 4.For adiabatic compression, ΔU = W, so the gas heats up
5.W = area under graph.
p2 T1 6.Ex. of adiabatic process: bicycle pump.

V1 V2 V

5. Cycle:

1 2 : work done by gas (isothermal change)


2 3: isochoric process (pressure decreases)
3 4: work done on gas (isothermal change)
4 1: isochoric process (pressure increases)

Net work done = area under 1 2 - area under 3 4

= area enclosed 1234.

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