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THERMAL PHYSICS
NOTES
3.1
Thermal Concepts
3.1.1
liquid
gas
3.1.2
Property
Particle behavior
Particles held close together by strong
forces and are stacked neatly in a
crystal lattice. Particles vibrate on the
spot with average kinetic energy much
less than the binding energy - energy
that must be absorbed for a particle to
break free.
Particles close but slightly further
apart than in a solid. Forces between
particles are weak allowing movement
of particles around each other. Average
kinetic energy of the particles is
similar in size to the binding energy.
Particles are far apart compared to
their size and exert virtually no force
on each other except during collisions.
Average kinetic energy much greater
than the energy binding them together
when in liquid state.
2.
These marks are named 0 oC and 100oC or 32oF and 212oF depending on the scale chosen. The
distance between the marks is divided up into 100 equal divisions for the Celsius thermometer
and 180 divisions for the Fahrenheit thermometer.
The Celsius scale is based on the temperature of melting ice being assigned the value zero. This
is an arbitrary zero. At 0oC, the H2O molecules still have thermal motion. Try dropping an ice
cube into liquid air. It causes the liquid air to boil! Recall that temperature is related to the
thermal motion of particles so it follows that absolute zero of temperature is when thermal
motion of particles ceases. The Kelvin temperature scale starts at absolute zero and each degree
is the same as the Celsius scale. Zero Kelvin is -273.14 oC but this is conveniently rounded off
to -273 oC. The word degree is omitted when using the Kelvin scale.
The following equivalences apply:
0K = -273 oC and 273K = 0oC
Thus Kelvin = Celsius + 273
3.1.3
Internal energy
The particles of a substance move and rotate. They have kinetic energy of motion and rotation.
Forces between particles means potential energy is stored in them. The total of the potential and
kinetic energies of the particles is called the internal energy of the substance.
Previously it was stated that temperature of a substance is related to the motion of its particles
More specifically, temperature is a measure of the average kinetic energy of the particles of a
substance and will be proven to be true later in this study. The temperature of a substance
determines if internal energy will be transferred to or from its surroundings.
Internal energy is the total of the kinetic and potential energies of the particles of the substance.
Conduction transfers internal energy within a substance and from one substance to another in
contact when a temperature difference exists.
During collisions, the particles with the greater kinetic energy slow down and the ones with
smaller kinetic energy speed up. The higher temperature substance cools and the lower
temperature substance warms up until the temperatures are the same. Solids are the best
conductors because the particles are stacked close together and collisions occur readily between
them. Gases are the poorest conductors because the particles are far apart and collisions between
them occur less often than in solids.
Heat is infra-red electromagnetic waves that travel at the speed of light. Thermal energy is the
energy transferred to or from a substance when heat is absorbed or radiated away. When heat is
absorbed, the internal energy of a substance increases. When heat is radiated away, its internal
energy decreases.
3.1.4
3.
The Specific Heat Capacity is the Heat Capacity of a specific mass of sample. This is either the
gram or the kilogram. Strictly speaking, SI units should involve the kilogram but the gram is in
common usage with Specific Heat Capacities. Thus the Specific Heat Capacity (SHC) is the
change in internal energy when 1 kg of a substance has its temperature changed by 1 oC. The
unit of SHC is Joule per kilogram per oC or Joule per gram per oC, written as J kg-1 oC-1 and
J g-1 oC-1.
The change in the internal energy of an object is equal to its specific heat capacity times its mass
times its change in temperature.
i.e. H = SHC x m x T
Some examples of substances and their Specific Heat Capacities are:
water 4200 J kg-1 oC-1
ice 2100 J kg-1 oC-1
lead 130 J kg-1 oC-1
The diagram opposite shows a direct way of
determining the Specific Heat Capacity of water. An
electric current raises the temperature of the heating
coil that causes an increase in the internal energy of
the water. The electrical energy transferred to heat
energy can be determined from the readings on the
meters and the heating time. The mass of the water
and its rise in temperature are measured. Assuming
complete transfer of electrical energy to internal
energy of the water, a value for the Specific Heat
Capacity of water can be calculated.
7 .0 V
3 .5 A
s tirre r
in s u la tio n
s te e l c a n
h e a tin g c o il
e.g. The arrangement above caused a 6.4 oC rise in
temp. when 100 g of water was heated for 2.0 min. Calculate the SHC of water.
Electrical energy transfer = 7.0 J C -1 x 3.5 C s-1 x 120 sec
= 2900 J
4.
The diagram opposite shows an indirect way of finding the SHC of copper.
The cube has been heated and its temperature measured. The cube was
placed in a calorimeter containing a known mass of water at a known
temperature. The temperature at equilibrium can be used to calculate the
SHC of copper.
e.g. The calorimeter used contained 80 mL of water at 15.0 oC. A 150 g
cube of copper was placed in a beaker of boiling water for several minutes.
The cube was removed and without delay, placed in the calorimeter. The
temperature at equilibrium was 26.5oC.
Internal energy decrease of Cu = SHC Cu x 0.15 x (100.0 - 26.5)
IE incr. of H2O + IE incr. of steel = SHCH O x 0.080 x (26.5-15.0) + 450 x 0.080 x (26.5-15.0)
= 4200 x 0.080 x 11.5 + 450 x 0.080 x 11.5
= 4.3 x 10 3 J
2
Assuming the internal energy decrease of Cu is equal to the internal energy increase of the H 2O
and the steel:
SHCCu x 0.15 x (100.0 - 26.5) = 4.3 x 103
SHCCu = 390 J kg-1 oC-1
The thermal capacity of the 150 g cube of copper = 390 x 0.150
= 58.5 J oC-1
3.1.5
Phase change
After it has been raining, the water on the ground evaporates. Evaporation of a liquid can occur
even though it is not boiling. A few of its particles have kinetic energy greater than the binding
energy and escape into the air. The temperature of the liquid can increase as it evaporates.
When the liquid is boiling, a large number of its particles have kinetic energy greater than the
binding energy and escape. Evaporation occurs at the fastest rate but the temperature remains
constant,
In a liquid, the average kinetic energy of the particles is similar in size to the binding energy.
Some of the particles have more kinetic energy than the average and some have less than the
average. Particles with more KE than the binding energy, move to the top of the liquid and
escape from its surface. This will occur even if the liquid is not boiling. When the particles with
more KE than average leave the liquid, the average KE of the particles remaining becomes
lower. Temperature is a measure of the average KE so evaporation of a liquid causes its
temperature to drop. This is why evaporation of perspiration cools your body.
Change
melting
evaporating
subliming
Substance behavior
As temperature increases, the solid
expands and when a certain
temperature is reached, the solid loses
its fixed shape and the material
becomes runny.
As temp. increases, the volume of
liquid gradually decreases. The amount
of the gaseous state increases in the
area above the liquid.
Particle behavior
As temp increases, particles vibrate
faster. Distance between particles
increases slightly and forces between
particles weaken. Binding energy and
av. KE become similar.
As temp. increases, particles vibrate
faster. When the KE of a particle
exceeds the binding energy, it moves
off by itself.
When a substance is changing state, its temperature remains the same. The internal energy
increases during the process, but this is hidden by the temperature remaining constant. This
hidden internal energy increase is called latent heat. The table on the next page summarises the
processes of internal energy increases for the melting of ice and the evaporation of water.
5.
Change
melting
evaporating
Substance behavior
When ice is melting, the
temperature of the ice/water
mixture remains at 0oC until all
the ice has melted
When water is boiling, its
temperature remains at 100oC. If
the evaporated steam is trapped in
a sealed container and heating
continues, the temperature will
rise above 100oC. A pressure
cooker does this.
Particle behavior
Heat energy must be absorbed if ice is to
melt. The internal energy of the molecules
increases during the melting process. The
internal energy absorbed does not increase
their average KE. It increases the potential
energy stored between the molecules.
Heat energy must be absorbed if water is to
evaporate. The internal energy of the
molecules increases during the evaporating
process. The internal energy absorbed does
not increase their average KE. It increases
the potential energy stored between the
molecules.
For a typical substance surrounded by normal air pressure, the graph of its temperature versus
heat energy added is shown below.
Bo il in g
Po int
Te m pe ra tu re
liqu id/g as
ga s
Liq u id
Me lt in g
Po int so lid
e vap o ratin g
H eat En e rg y
c on de nsin g
The state of a substance depends on both its temperature and the pressure of the air around it.
The graph of pressure versus temperature shows the conditions when it will be a solid a liquid
or a gas.
melt
critic al
po int
liquid
Pre ssu re
fre eze
c on den se
s olid
va po riz e
trip le
po int
d ep ose
su blime
gas
Temp er atu r e
The triple point marks the only temperature and pressure that the solid, liquid and gas states can
exist together. The critical point marks the temperature that if exceeded, increasing the pressure
will not cause the gas to become a liquid. The molecules might be very close but no horizontal
surface forms. Deposition is when a gas changes straight to a solid. It occurs in clouds
when water vapour turns into snowflakes when the temperature and pressure are low enough.
6.
For carbon dioxide, the triple point is at -56 OC and 5.1 atmosphere. Therefore when placed on
the table and warming up at 1 atmosphere of pressure, it will sublime.
For water, the triple point is at 0 OC and 0.006 atmosphere. Therefore when ice is placed on
the table and warming up at 1 atmosphere of pressure, it will melt.
Freeze dried food is created by freezing the food so the water content turns into solid ice. Then,
the air pressure around the food is dropped sufficiently and warmed slightly until the ice
sublimes and leaves the food as water vapour. This makes the food light for hikers to carry but
free from bacteria that would multiply if the water content were removed by strongly heating it.
3.1.6
3.2
Modelling a gas
3.2.1
Pressure.
The pressure on a surface is equal to the force on the surface divided by its area. P = F/A. The
unit of pressure is N m-2. A pressure of 1 N m-2 is called 1 Pascal Pa.
Imagine a very thin sheet of plywood with a mass of 100 g and an area of 1 m 2. The wood
weighs about 1 N. When the wood lies flat on the floor it applies a pressure of 1 Pa on the floor.
The Pascal is a small unit. Air applies a force of about 10 N on each cm 2. This amounts to
about105 N m-2 or 105 Pa. The unit kiloPascal kPa is used frequently. Normal air pressure is
about 101 kPa.
The walls of a container are continually bombarded by fast moving gas molecules. When a
molecule bounces off the wall, it pushes outward against the wall and the wall pushes inwards
on the molecule. Each molecule is very tiny and many collisions occur each second. It seems
that the container is receiving a constant outward force. The force per square metre of area is the
pressure of the gas.
3.2.2
7.
The kinetic model of an ideal gas assumes:
*
*
*
*
that a gas consists of a large number of very small particles that are far apart and are
moving randomly in all directions with a range of speeds. The average kinetic energy of
the particles is a measure of the gas's temperature.
the particles obey the laws of mechanics.
The particles exert no force on each other except during collisions.
When a particle collides with the container wall or another particle it bounces off making
an elastic collision. During impact the particle applies a force to the container and the
container applies a force back on the particle. The net outward force of all the particles on
the container wall gives rise to the pressure of the gas.
Real gas exert molecules small forces on each other between collisions. When a gas is
compressed or its temperature is low the gas is is close to being a liquid, it does not show ideal
behavior.
3.2.3
3.2.4
8.
The pressure of a gas is also affected by the mass of the gas. The greater the mass of gas, the
more particles present and the more collisions that occur with the walls of the container each
second. If the volume remains the same as in pumping up a tyre, the pressure increases. If the
pressure remains the same, the volume increases.
A bike pump is a cylinder of gas with a piston. Putting your finger over the hole and pushing in
the piston increases the pressure on the air in the pump. When the pressure on the air is
increased, the volume of air decreases. When the volume decreases, the molecules travel less
distance before colliding with the walls. More collisions occur with the walls each second. The
outward force on the container increases and the pressure of the air inside the pump increases.
The movement of the piston down on the gas does work on the gas. The gas molecules bounce
off the moving piston with a faster speed just like a ball that is hit by a moving tennis racquet.
The Temperature of the gas increases as the average kinetic energy of the gas molecules has
increased. Conduction of heat energy to the surroundings results in a decrease in internal energy
of the gas. When the piston is pulled back (finger still on the hole) the temperature of the gas is
lower than its initial value. This is the principle that fridges use to operate.
All the discussions above indicate there is a connection between the pressure, temperature,
volume and mass of a gas.
The walls of a container are continually bombarded by fast moving gas molecules. When a
molecule bounces off the wall, it pushes outward against the wall and the wall pushes inwards
on the molecule. Each molecule is very tiny and many collisions occur each second. It seems
that the container is receiving a constant outward force. The force per square metre of area is the
pressure of the gas.
The pressure on a surface is equal to the force on the surface divided by its area. P = F/A. The
unit of pressure is N m-2. A pressure of 1 N m-2 is called 1 Pascal Pa. The Pascal is a small unit.
Air applies a force of about 10 N on each cm 2. This amounts to about105 N m-2 or 105 Pa. The
unit kiloPascal kPa is used frequently. Normal air pressure is about 101 kPa.
1 /P
P
The diagram shows a gas inside a container that has a
piston free to slide. The piston will stop in the
position where the gas pressure inside the container
is the same as atmospheric pressure. When the gas
is heated, its pressure will remain constant and its
volume increases as the piston slides.
a ir
gas
Jacques Charles discovered around 1800 that the volume of the gas increased in equal amounts
for equal rises in temperature. This is now described as volume is directly proportional to its
absolute Temperature (measured in K) V T when P constant. This is called Charles' Law.
If a gas is in a sealed container with a fixed volume, the pressure of the gas increases when its
temperature increases. When the temperature increases, the average KE of the particles
increases. More collisions occur with the walls each second and the collisions are more forceful.
The outward force on the container increases. The air pressure in a cold car tyre is lower than it
pressure after the car has been driven and the tyre has increased temperature. Recommended
tyre pressures apply when the tyre is cold.
9.
Joseph Gay-Loussac found that for a gas with constant volume, its pressure is directly
proportional to its absolute temperature i.e. P T when V constant. This is Gay-Loussac's Law.
The three Gas Laws just described are not true laws in that they are only true for ideal gases.
They are good approximations when applied to a real gas that is not close to becoming a liquid
when pressure is high or temperature is low.
Combining the relationships discussed so far gives:
PV T
PV = KT
Adding more molecules to a sample of gas means more collisions with the walls and pressure
would increase. For the pressure and temperature to remain the same, the volume increase to
reduce the frequency of molecules hitting the walls of the container. In the last equation, if P
and T remain constant and the number of molecules increases, the value of K must increase
also. Thus K is proportional to the number of molecules N.
K = kN
PV = kNT
When at the same temperature and pressure, the number of molecules per m 3 is the same for all
gases. Therefore the constant k is the same for all gases i.e. it is a universal constant.
v
m
vt
Vo lum e V
Ar ea o f side s A
v.
Assuming the molecule bounces off the wall at the same speed:
v=2 v
10.
In the time t it takes the molecule to reach the wall, if n molecules hit the wall, the average
impulse applied to the wall is:
F t = 2m v x n
The volume of the gas between the dotted line and the right hand wall is vt x A
This volume is the fraction vtA/V of the total volume. Therefore the number of molecules in
this volume is N x vtA/V.
However half the molecules in this volume will be moving away from the wall. Therefore the
number of molecules n that collide with the wall in time t is 0.5NvtA/V. Substituting the value
of n into the impulse equation gives:
F t = 2mv x 0.5NvtA/V
F = Amv2 x N/V
The pressure P of the gas on the wall is force F divided by area A. Therefore:
P = mv2 x N/V
This last line was calculated assuming all the molecules were travelling directly towards the
wall. Call this the x direction. The last equation becomes:
P = mvx2 x N/V
However, the molecules will be moving in random directions. Molecules will have velocity
components in the x, y and z directions.
For a molecule with velocity v, its components have magnitudes vx, vy and vz. Applying
Pythagoras in 3-D gives:
v2 = vx2 + vy2 + vz2
Given the randomness of the motion of a large number of molecules, the average values of vx2,
vy2 and vz2 should be equal. Therefore:
v2av = 3 vx2av
vx2av = 1/3 v2av
hence
hence
/3 x KEav x N = kNT
hence
KEav = 3/2kT
The average kinetic energy of the gas molecules is directly proportional to its absolute
temperature. The opposite viewpoint is the temperature of a gas is a measure of the average
11.
What is the average speed of an air molecule at 20 oC?
Most of the air is nitrogen. The mass
of a nitrogen molecule N2 is 4.65 x 10-26 kg. The absolute temperature is 293 K.
KEav = 3/2kT
mvav2 = 3/2kT
-26
x 4.65 x 10 x vav2 = 1.5 x 1.38 x 10-23 x 293
vav = 511 m s-1
Ever wondered why the hair of people sitting behind the windscreen of an opened topped car is
blown forward!!!? The air molecules are rushing into the space behind the windscreen faster
than the car and its passengers are travelling. Wear a hat or you will have a sore scalp.
The pressure of a gas is affected by the mass of the gas. When V 1/P, V T and V m are
combined, then PV mT. As an equation PV = mT where (kappa) is a constant.
Consider the following information about gases at STP - 0 oC and 1 atmosphere:
Gas
mass kg
Volume m3
no. of mole
oxygen
hydrogen
carbon dioxide
0.032
0.002
0.044
0.0224
0.0224
0.0224
1
1
1
Each gas has the same volume 0.0224 m3, the same temperature 273 K, the same pressure
1.01 x 10-5 N m-2 but a different mass in kg. Hence if the information for each gas is substituted
into the equation PV = mT, a different value for would be obtained for each gas.
However, the number of mole is the same for each gas. If the mass is measured in number of
mole n, a new constant R will apply. i.e. PV = RnT. All gases in the table have the same values
for P, V, n and T so R is a universal constant.
PV = RnT
1.01 x 105 x 0.0224 = R x 1 x 273
R = 8.3 J mol -1 K-1 called the universal gas constant
By tradition the ideal gas equation is written as PV = nRT.
In a closed container, the mass of gas remains constant. Therefore:
PV/T = nR
= constant for the same no. of mole
Previously it was established that PV = 2/3 KEav x N where KEav is the average kinetic energy of
a single molecule and N is the total number of molecules.
Comparing this to the ideal gas equation PV = RnT means:
2
rearranging
/3 KEav x N = nRT
KEav = 3/2 x n/N x RT
The total kinetic energy of all the molecules is N times the last equation i.e.
KEtotal = 3/2nRT
One mole is the mass of 6.023 x 1023 molecules of the gas. The number 6.023 x 1023 is called
Avogadro's constant NA. If 3.012 x 1023 molecules are present, the mass is 0.5 mol. Hence the
number of mole is equal to the number of molecules present divided by Avogadro's constant
i.e. n = N/NA. Rearranging, n/N = 1/NA. Substituting into the second last equation gives:
KEav = 3/2 RT/NA
12.
What is the average kinetic energy of a gas molecule at 20 oC?
Using KEav = 3/2kT
In a sealed container, the mass of the gas remains constant. This means PV/T = nR i.e. PV/T is a
constant. For two different sets of P, V and T values, this is usually written as:
P1V1/T1 = P2V2/T2
You will be expected to solve problems involving the ideal gas equation. Pressure gauges
measure the pressure difference between the gas pressure inside a container and the air outside.
If a gauge reads 1atmosphere, the pressure inside the container is one atmosphere higher than
the air outside. The pressure of the gas inside the container is 2 atmospheres. This is called the
absolute pressure. Thus absolute pressure equals gauge pressure plus 1 atmosphere.
3.2.5
Ideal
Thermal Physics.