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THERMAL PHYSICS
Thermal concepts
3.2
PHLOGISTON/CALORIC THEORY
CORE
3.1
COUNT RUMFORD
Much of the credit for dismantling the idea that heat was
motion rather than substance or caloric goes to Benjamin
Thompson (1753 1814), also known as Count Rumford of
Bavaria.
During the American Revolution, he was a Tory or loyalist
in the disputes between Britain and its American colonies
serving as a major in a company of militia. It is believed
that he invented a cork flotation system for cannons while
being transported by horses across rivers. He also designed
a gun carriage that could be carried by three horses and
could be assembled ready for firing in 75 seconds. He
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CHAPTER 3
CORE
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THERMAL PHYSICS
that he could measure the temperature with a precision of
a fraction of a degree.
Example
ywheel
spindle
to pulley with
weights attached
to pulley with
weights attached
moving vanes
CORE
handles
Solution
calorimeter
(containing water)
xed vanes
= 10 g 1 cal 46.8 C
1.96 10 J
W
----- = --------------------------------2
Q
4.68 10 cal
= 4.19 J cal-1
The mechanical equivalent of heat for water is 4.2 J cal -1.
Joule found that about 4.2 joules of work would yield one
calorie of heat or that the quantity of heat required to
raise the temperature of one gram of water by 1 C is one
calorie.
A modern day value for the mechanical equivalent of heat
is 4.18605 joules = 1 calorie.
The experiments proved beyond doubt that mechanical
work can produce heat and as such no caloric fluid can
be created or destroyed. Furthermore, Joule reasoned that
the temperature increase must be related to the energy of
the microscopic motions of the particles.
Finally, a paradigm shift in our way of reasoning had again
proved that science is not the ultimate truth.
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CHAPTER 3
CORE
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THERMAL PHYSICS
points). For example, different thermometers will give
different values for the boiling point of zinc (907 C).
100C
capillary tube
glass
stem
0 C
mercury or alcohol
thin glass
bulb
CORE
vacuum
T in K = T in C + 273.16
Exercise
A clinical thermometer as shown in Figure 303 does not
need the temperature range of a laboratory thermometer.
It is designed so that the maximum temperature remains
constant after the patients temperature is taken. It has a
small constriction to stop the mercury flowing back into
the bulb. The mercury is then shaken back into the bulb
after the temperature has been taken.
1.
35
36
37
38
39
40
41
42
C.
Figure 303 A Clinical Thermometer
D.
In order to calibrate these thermometers, two fixed points
are used to define the standard temperature interval. The
ice point (the lower fixed point) marked at 0 C is the
temperature of pure ice at standard atmospheric pressure
and is in thermal equilibrium with the liquid in the bulb.
The steam point (the upper fixed point) marked at 100 C
is the temperature of steam at standard atmospheric
pressure and is in thermal equilibrium with the liquid in
the bulb. The scale between these values is marked with
even spaces. The Celsius temperature scale named after
the Swedish astronomer Anders Celsius (1701-1774) is
constructed in such a manner.
Although thermometers constructed using thermometric
properties are useful for everyday use, they are not
accurate enough for scientific work. Unfortunately, two
thermometers constructed using different thermometric
properties do not necessarily agree with each other as they
do not vary linearly over large temperature ranges. (They
are of course in agreement at the lower and upper fixed
3.1 (a)
2.
3.
4.
5.
6.
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CHAPTER 3
7.
8.
CORE
Potential energy, U / J
gas
equilibrium separation
separation, r / m
r0
liquid
solid
minimum potential energy =
Ep
F = ____
r
In other words, the gradient of the potential energy curve
at any point on the curve gives the force that must be
applied to hold the molecules at that separation. We can
classify the phases according to the sizes of the energy .
Force, F / N
repulsion
nuclear separation, r / m
10r 0
r0
attraction
gaseous phase
Figure 304
Vibrational
kinetic energy
Figure 306
Rotational
kinetic energy
Translational
kinetic energy
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THERMAL PHYSICS
TEMPERATURE
At the macroscopic level, temperature is the degree
of hotness or coldness of a body as measured by a
thermometer. Thermometers are made using the
thermometric properties of a substance such as:
CORE
TEMPERATURE
INTERNAL ENERGY
As already mentioned, internal energy is the sum total of
the potential energy and the random kinetic energy of the
molecules of the substance making up a system. In order
to apply the Law of conservation to thermal systems, one
has to assume that a system has internal energy.
At the macroscopic level, it can be observed that molecules
are moving. When pollen (a fine powder produced by
flowers) is sprinkled on the surface of water and the setup is viewed under magnification, it can be seen that the
pollen particles carry out zig-zag motion called Brownian
Motion. Their motion is caused by the kinetic energy of
the water molecules. Walking past a coffee shop you smell
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CHAPTER 3
CORE
Convection tube
water
Heat
Figure 307
Potassium
permanganate
crystal
Convection current.
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THERMAL PHYSICS
101.3 kPa pressure (STP) and contains 6.02 10 23
particles.
1.
64.0 g
m = _________________
n = __
= 2 mol
M ( 16.0 + 16.0 ) g mol1
2.
CORE
Solution
+
4
Volume
= 2 mol 22.4 dm3
m
n = __
M
= 44.8 dm3
4.
m=nM
where
= 33 g
Example
1.
2.
3.
4.
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CHAPTER 3
6.
Exercise
1.
CORE
B.
C.
D.
3.
B.
C.
D.
7.
8.
A.
B.
C.
D.
16
8
4
2
3 1023
6 1023
12 1023
24 1023
(b)
11.
100 g of copper
5.0 g of oxygen molecules
100 g of calcium carbonate, CaCO3
4.4 g of carbon dioxide
13.88 g of lithium
10.
Cl2
HCl
CuSO4
Na2CO3
CH4
9.
3 1023
6 1023
12 1023
24 1023
5850 mol
0.585 mol
1.71 mol
41.5 mol
4.
2.
3.1 (b)
volume
specific heat capacity
kinetic energy of a particle
pressure
temperature
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THERMAL PHYSICS
Example
CORE
Solution
Q = Thermal capacity T
3
( 61 25 ) C
36 C
= 3.2 10 JK
= 3.2 10 JK
= 115200J
= 1.2 10 J
3.2.8 Solve problems involving specic latent
heats.
IBO 2007
Heat capacity does not take into account the fact that
different masses of the same substance can absorb or
release different amounts of thermal energy.
Zinc
Lead
Q
Thermal Capacity = ___ J K -1
T
Q is the change in thermal energy in joules J
CA NDL E WAX
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CORE
CHAPTER 3
The aluminium block melts the most wax and the lead
melts the least. Therefore, the metals of the same mass
give out different amounts of thermal energy in a certain
time period. This can be explained from a microscopic
viewpoint. The kilogram unit masses have different
numbers of particles of different types and masses. The
metal blocks were given the same amount of thermal
energy when they were heated to 80 C. When the thermal
energy gained by each metal is distributed amongst its
particles, the average energy change of each particle will
be different for each metal.
Example
Solution
Q
c = _____
mT
Example
Q = m c T
Q = the change in thermal energy required to produce a
temperature change in Joules, J.
m = mass of the material in grams (g) kilograms (kg)
T = the temperature change in Kelvin, K.
Note that T is always positive because heat always
transfers from the higher temperature region to the lower
temperature region.
For gases, the molar heat capacity at constant volume Cv
and the molar heat capacity at constant pressure Cp are
more commonly used. Molar heat capacity is the quantity
of heat required to raise the temperature of one mole of the
gas by one degree Kelvin under the constant condition.
Figure 309 shows the specific heat capacity for some
common substances at room temperature (except ice)
Substance
Lead
Mercury
Zinc
Brass
Copper
Figure 309
Specific heat
J kg -1 K -1
2
1.3 10
1.4 102
3.8 102
3.8 102
3.85 102
Substance
Iron
Aluminium
Sodium
Ice
Water
Specific heat
J kg -1 K -1
2
4.7 10
9.1 102
1.23 103
2.1 103
4.18 103
Solution
2.553 106 J
Tf = ______________
2.09 105 ( J K1 )
Tf = 12.26 C
Tf = 12 C
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CORE
THERMAL PHYSICS
stirrer
joulemeter
thermometer
copper vessel
heating coil
lagging
Temperature, C
liquid
theoretical curve
3
2
1
(= correction)
( = 2 1 )
actual curve
A1
A2
A
= -----1- , so that 3 = 2 +
A2
room
temp
2t
Figure 311
3t
Time, minutes
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CHAPTER 3
We also have that,
thermometer
V
immersion
heater
CORE
metal block
Low voltage
supply
lagging
Example
The final temperature of the water is 28 C
A block of copper of mass 3.0 kg at a temperature of
90 C is transferred to a calorimeter containing 2.00 kg of
water at 20 C. The mass of the copper calorimeter cup is
0.210 kg. Determine the final temperature of the water.
Exercise
1.
Solution
3.2 (a)
1.6 107 J
1.6 105 J
4.4 107 J
4.4 105 J
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9.
10.
11.
12.
13.
thermometer
V
immersion
heater
metal block
lagging
Low voltage
supply
m
VI
VI
c=
m
VIt
c=
m
m
c=
VIt
c=
(i)
(ii)
(iii)
3.
4.
5.
(iv)
(v)
6.
7.
8.
14.
15.
16.
CORE
THERMAL PHYSICS
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CORE
CHAPTER 3
17.
18.
solid
liquid
gas
Liquid
Variable
Definite
Very slightly
Compressible
Slow
Gas
Variable
Variable
Highly
Compressible
Fast
High
Low
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Kinetic energy
Potential energy
Mean molecular
Separation (r0)
Thermal energy
of particles ()
Molecules per m3
Solid
Vibrational
High
Liquid
Gas
Mostly
Vibrational translational
Rotational
Higher
rotational
Some
translational Higher
vibrational
Higher
Highest
r0
r0
10r0
< /10
>
1028
1028
1025
CORE
THERMAL PHYSICS
CHANGES
A substance can undergo changes of state or phase changes
at different temperatures. Pure substances (elements and
compounds) have definite melting and boiling points
which are characteristic of the particular pure substance
being examined. For example, oxygen has a melting point
of -218.8 C and a boiling point of -183 C at standard
atmospheric pressure.
The heating curve for benzene is illustrated in Figure 317.
A sample of benzene at 0C is heated in a closed container
and the change in temperature is graphed as a function
of time. The macroscopic behaviour of benzene can be
described using the graph and the microscopic behaviour
can be interpreted from the macroscopic behaviour.
Temperature /C
L iquid-gas phase
change
boiling 80C
point
G AS
Solid-liquid
phase change
melting
point 5.5C
L I QUID
SO L I D
Heating time /min
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CHAPTER 3
CORE
PHASE CHANGES
The moving particle theory can be used to explain the
microscopic behaviour of these phase changes. When
solid benzene is heated the particles of the solid vibrate
at an increasing rate as the temperature is increased.
The vibrational kinetic energy of the particles increases.
At the melting point a temperature is reached at which
the particles vibrate with sufficient thermal energy to
break from their fixed positions and begin to slip over
each other. As the solid continues to melt, more and
more particles gain sufficient energy to overcome the
forces between particles and over time all the solid
particles change to a liquid. The potential energy of
the system increases as the particles begin to move. As
heating continues the temperature of the liquid rises
due to an increase in the vibrational, rotational and
part translational kinetic energy of the particles. At
the boiling point a temperature is reached at which the
particles gain sufficient energy to overcome the interparticle forces present in the liquid benzene and escape
into the gaseous state. Continued heating at the boiling
point provides the potential energy needed for all the
benzene molecules to be converted from a liquid to a
gas. With further heating the temperature increases
due to an increase in the kinetic energy of the gaseous
molecules due to the larger translational motion.
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THERMAL PHYSICS
1.
C.
D.
2.
5.
A.
B.
D.
6.
watt
the product of the newton and the metre
the quotient of the watt and the second
the product of the joule and the second
20
63 Jkg-1K-1
105 Jkg-1K-1
126 Jkg-1K-1
504 Jkg-1K-1
7.
8.
15
10
A.
T ime / min
C.
D.
4.
B.
C.
3.
50
3.2 (b)
100
CORE
Exercise
150
Temperature / oC
(a)
(b)
(c)
9.
10.
11.
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CORE
CHAPTER 3
12.
(a)
(b)
13.
14.
15.
Convert 63 C to Kelvin
Convert 52 K to degrees Celsius
16.
17.
18.
T H E R M A L E NE R G Y A DDE D
sublimation
melting
SOL I D
evaporation
L I QUI D
freezing
GAS
55
159
600
1356
273
0.14
1.05
0.25
1.8
3.34
90
351
1893
2573
373
2.1
8.7
7.3
73
22.5
condensation
Example
Figure 320 Macroscopic
transformations between states of matter.
Sublimation is a change of phase directly from a solid to
a gas or directly from a gas to a solid. Iodine and solid
carbon dioxide are examples of substances that sublime.
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The latent heat of vaporisation can be found using a selfjacketing vaporiser as shown in Figure 323. The liquid
to be vaporised is heated electrically so that it boils at a
steady rate. The vapour that is produced passes to the
condenser through holes labelled H in the neck of the
inner flask. Condensation occurs in the outer flask and
the condenser.
Solution
CORE
THERMAL PHYSICS
Example
H
Vapour acting as
a jacket
Liquid under
investigation
Heating coil
Wa ter outflow
Solution
C ondenser
C old water
C ollecting vessel
Using
C ondensed vapour
T H E R M A L E NE R G Y R E L E A SE D
L atent heat of fusion
I C E at
7C
L I Q U I D water at
0 C
Specific heat I ce
0 C
100 C
G ASE OU S water at
100 C
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CHAPTER 3
apparatus will be at the same temperature as it was with
the initial rate vaporisation.
4.
Therefore:
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
CORE
V2I2t = m2LV + H
By subtracting the two equations:
(V1I1 V2I2)t = (m1 m2)LV
From this equation, the value of the latent heat
of vaporisation of the unknown substance can be
determined.
Exercise
1.
2.
A.
B.
C.
D.
3.
3.2 (c)
Average kinetic
energy
Average potential
energy
constant
increases
increases
constant
increases
constant
decreases
constant
5 C to 20 C
15 C to 35 C
75 C to 90 C
95 C to 101 C
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THERMAL PHYSICS
3.2.9 PRESSURE
Investigations into the behaviour of gases involve
measurement of pressure, volume, temperature and mass.
Experiments use these macroscopic properties of a gas to
formulate a number of gas laws.
CORE
P = F /A
The SI unit of pressure is the pascal Pa.
1 atm = 1.01 105 Nm-2 = 101.3 kPa = 760 mmHg
IDEAL GAS
An ideal gas is a theoretical gas that obeys the ideal gas
equation exactly. Real gases conform to the gas laws under
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CHAPTER 3
CORE
1
3
E k = --- mv 2 = --- kT where k = Boltzmann constant
2
2
v 2 T
The term average kinetic energy is used because, at a
particular temperature different particles have a wide
range of velocities, especially when they are converted to a
gas. This is to say that at any given temperature the average
speed is definite but the velocities of particular molecules
can change as a result of collision.
Figure 325 shows a series of graphs for the same gas
at three different temperatures. In 1859 James Clerk
Maxwell (1831-1879) and in 1861 Ludwig Boltzmann
(1844-1906) developed the mathematics of the kinetic
theory of gases. The curve is called a Maxwell-Boltzmann
speed distribution and it is calculated using statistical
mechanics. It shows the relationship between the relative
number of particles N in a sample of gas and the speeds v
that the particles have when the temperature is changed.
(T3 > T2 > T1)
The graphs do not show a normal distribution as the
graphs are not bell-shaped. They are slightly skewed to
the left. The minimum speed is zero at the left end of
the graphs. At the right end they do not touch the x-axis
because a small number of particles have very high speeds.
N
T1
T2
v rms =
T1
T2
T2 > T1
Ek
T3 > T2 > T1
T3
v ms
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THERMAL PHYSICS
AN IDEAL GAS
Robert Boyle (1627-1691) discussed that the pressure of a
gas at constant temperature is proportional to its density.
He also investigated how the pressure is related to the
volume for a fixed mass of gas at constant temperature.
Boyles Law relates pressure and volume for a gas at fixed
temperature.
capillary tube
Boyles Law for gases states that the pressure of a fixed mass
of gas is inversely proportional to its volume at constant
temperature.
bead of acid
(e.g. sulfuric acid)
water bath
1 PV = constant
P __
V
CORE
air column
H E A T
P1V1 = P2V2
Figure 328
pressure, P mm Hg
pressure, P mm Hg
PV
273
0
volume, V cm 3
Figure 327
V cm3
1 cm3
V
0 100
273 373
T C
T K
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CHAPTER 3
CORE
V
V T V = kt so that ___1 = k
T1
Therefore,
V1 ___
V
___
= 2
T1 T2
As the temperature of a gas is increased, the average kinetic
energy per molecule increases. The increase in velocity
of the molecules leads to a greater rate of collisions, and
each collision involves greater impulse. Hence the volume
of the gas increases as the collisions with the sides of the
container increase.
Experiments were similarly carried out to investigate the
relationship between the pressure and temperature of a
fixed mass of various gases.
The essential parts of the apparatus shown in Figure 330
are a metal sphere or round bottomed flask, and a
Bourdon pressure gauge. The sphere/flask and bourdon
gauge are connected by a short column of metal tubing/
capillary tube to ensure that as little air as possible is at a
different temperature from the main body of enclosed gas.
The apparatus in Figure 330 allows the pressure of a fixed
volume of gas to be determined as the gas is heated.
Bourdon gauge
273
0
0 100
273 373
T C
T K
P1
P T P = kT------ = k
T1
Therefore,
P
P
-----1- = -----2T1
T2
As the temperature of a gas is increased, the average kinetic
energy per molecule increases. The increase in velocity of
the molecules leads to a greater rate of collisions, and each
collision involves greater impulse. Hence the pressure of
the gas increases as the collisions with the sides of the
container increase.
counter-balance
metal stem
thermometer
retort
stand
air enclosed
in a metal
sphere
Figure 330
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