FC312E

PHYSICS
Theme: 8 Hour: 1 Thermodynamics
Module Learning Outcome Academic Literacy
Use ideal gas law Use theoretical concepts to analyse real-world
practices. 
Apply in real-world contexts Develop ability to read, comprehend and express
mathematical arguments
Use subject-specific vocabulary effectively.
IDEAL GAS LAW
Pressure, Volume, Temperature
 Gases
• Gases
  can be pictured
microscopically as atoms bouncing
around but their macroscopic
properties are easier to work with:
• Pressure: the force atoms exert over a
certain area in the container ( ), measured
in Pascals, .
• Volume: The 3D space occupied by the
gas, measured in .
• Temperature: macroscopic quantity that
ultimately relates to how much kinetic
energy the atoms have at microscopic
level, measured in Kelvin, .
 Ideal Gases
• Gases are the easiest state of matter to describe, as
all ideal gases exhibit similar behavior.
• An ideal gas is one that is thin enough, and far away
enough from condensing, that the interactions
between molecules can be ignored.
Pressure
 Ideal Gas Law
•• The
  idealised relationship between pressure , volume
and temperature is the ideal gas equation:

• Sometimes this is written slightly differently as:

Where:

 
 Moles
•  In Chemistry and Physics a unit called a
mole is used.

• We call this special number of atoms in a

mole is Avogadro’s Constant,
• So in general if we have moles in a
substance the number of molecules/atoms is:
 Molar Mass
• The atomic or molecular mass of a substance is the
mass, in grams, of one mole of that substance. For
example,
• Helium:
• Copper:
• Furthermore, the mass of an individual atom is given
by the atomic mass divided by Avogadro’s number:
 Molar Mass
• The
  molar mass of a substance is the mass of 1
mole (i.e. the mass of molecules of the
substance)
• So if we have moles of a substance with molar
mass then we can get the total mass of those
moles by doing:
 Boyle’s Law
• If
  we take the ideal gas law from earlier and
divide both sides by the formula is:

• So for an ideal gas. From this, we get a few

important ‘laws’.
• Boyle’s law says that if an experimentalist
can fix the temperature of a gas as the
pressure and volume change then:
Boyle’s Law for Ideal Gases
Boyle’s law, which is
consistent with the ideal
gas law, says that the
pressure varies inversely
with volume. These
curves of constant
temperature are called
isotherms.
 Charles’ Law for Ideal Gases
•• Since:
 

• for an ideal gas, we can see that there is a similar law to

Boyle’s law when a gas is changed at constant pressure.
• This is called Charles’ Law written as:

In other words:
 Charles’ Law for Ideal Gases
Charles’s law, also
consistent with the
ideal gas law, says
that the volume of a
gas increases with
temperature if the
pressure is constant.
MEASURING ABSOLUTE ZERO
with a constant-volume gas thermometer

Pgas=Patm+rgh

V  const N  const
PV  Nk BT
P Nk B
  const
T V
If the volume of a gas is constant, its
pressure is linearly proportional to its
P  const T temperature
 Ideal Gases
If the volume of an ideal
gas is held constant, we
find that the pressure
increases with
temperature:
 Ideal Gases
If the volume and temperature are kept constant,
but more gas is added (such as in inflating a tyre or
football), the pressure will increase:
 Ideal Gases
If the temperature is constant and the volume
decreases, the pressure increases:
 Ideal Gases
In this photograph, the
balloon was inflated at
room temperature and
cooled with liquid
nitrogen. The decrease
in volume of the air in
the balloon is obvious.
Maxwell-Boltzmann Distribution
 Kinetic Theory of Gases
The kinetic theory relates microscopic quantities
(position, velocity) to macroscopic ones (pressure,
temperature). Assumptions:
– N identical molecules of mass m are inside a
container of volume V; each acts as a point
particle.
– Molecules move randomly and always obey
Newton’s laws.
– Collisions with other molecules and with the walls
are elastic.
 Kinetic Theory of Gases
• Pressure is the result
of collisions between
the gas molecules
and the walls of the
container.

• It depends on the mass and speed of the molecules,

and on the container size:
 Kinetic Theory of Gases
• We replace the speed in the previous expression for
pressure with the average speed:

• Including the other two directions,

• Therefore, the pressure in a gas is proportional to

the average kinetic energy of its molecules.
 Kinetic Theory of Gases
•• The
  molecules of a gases all move around in a chaotic way
(so-called ‘brownian motion’)
• Different molecules will have different speeds . These
speeds follow what is called a ‘Maxwell-Boltzmann’ type
distribution:
 

 
 Kinetic Theory
Not all molecules in a gas will have the same speed; their
speeds are represented by the Maxwell distribution, and
depend on the temperature and mass of the molecules.
 Kinetic Velocity of Molecules

• is  the ‘root mean square’ velocity, defined in

terms of the velocities of each molecule (for
molecules in gas) as:

This gives a very useful average velocity

since it allows us to write the mean kinetic
energy of a gas molecule:
Kinetic Velocity of Molecules
The RMS speed, vrms is slightly greater than the most
probable speed, vmp and the average speed, vav.
 Kinetic Theory equation
•• A long derivation that we omit in this course can prove a very
 
important equation that shows the relationship between the and
the pressure and volume of the gas:

• Recalling the ideal gas law we can equate the left hand side of
these equations:

(multiply by )
 Kinetic Energy
•This
  last equation is worth looking at more:

Speed increasing with temperature

This equation shows
how the kinetic energy
of molecules is
proportional to the
temperature.
 Kinetic Energy: Example
•Use
  the formula:

To find the root mean square speed for four gas

molecules with speeds:
 Kinetic Energy: Example
•Just
  inserting the velocities into the formula with
gives:
 Kinetic Energy: Example
•Calculate
  the root mean square of oxygen molecules
at .
You will need the molar mass of oxygen which is:
Also note the constants:
 Kinetic Energy: Example
•First
  of all don’t forget that temperature is in
Kelvin so .
Now to get the mass of an oxygen molecule.
We know the mass of one mole is 0.032 kg
so if we divide by the number of molecules in
a mole (, hence:

Now we use the key equation:

 Internal Energy of a Gas
• As we have seen the mean kinetic energy for one gas
•  molecule for a gas of temperature is:

• And so if we have gas molecules the total energy also called

the internal energy is:

• Since and we can rewrite this in more common form:

 Phase Equilibrium & Evaporation
A liquid in a closed container will come to equilibrium with its
vapour. However, an open liquid will not, it will continue to
vapourize without reaching equilibrium.
The molecules that escape from the liquid are the higher
energy ones, this has the effect of cooling the liquid. This is
why sweating cools us off.
Phase Equilibrium & Evaporation
If we look at the Maxwell speed distributions for water at
different temperatures, we see that there is not much
difference between the 30° C curve and the 100° C curve.
This means that, if 100° C water molecules can escape,
many 30° C molecules will escape also.
 Phase Equilibrium & Evaporation
This same evaporation process can cause a planet to lose
its atmosphere – some molecules will have speeds
exceeding the escape velocity. The evaporation process will
be faster for lighter molecules and for less massive planets.
 FIRST LAW OF
THERMODYNAMICS
 Zeroth Law of Thermodynamics

If object A is in thermal
equilibrium with object B, and
object B is separately in
thermal equilibrium with
object C, then objects A and C
will be in thermal equilibrium
if they are placed in thermal
contact.
 First Law of Thermodynamics
The first law of thermodynamics is a statement of the
conservation of energy.
If a system’s volume is constant, and heat is added, its internal
energy increases.
 First Law of Thermodynamics
If a system does work on the external world, and no heat is added,
its internal energy decreases.
 First Law of Thermodynamics
1- Heat added to the system
2- Work done by the system

The change in a system’s internal energy is related to the heat Q and

the work W as follows:

U = Q - W
It is vital to keep track of the signs of Q and W.

• Systems gains heat Q + ive

• Systems loses heat Q  ive
• Work done by the system W - ive
• Work done on the system W + ive
 First Law of Thermodynamics
Systems gains heat, Q
+ ive, T2 > T1
Molecules with higher
temperature move faster

Work done
on the system

W - ive, V2 < V1
 First Law of Thermodynamics
The internal energy of the system depends only on its
temperature. The work done and the heat added, however,
depend on the details of the process involved.

Systems loses heat,

Q = -ive

Work done by the system,

W = +ive

There is a loss in energy,

Ui > Uf
 Thermal Processes
We will assume that all processes we discuss are quasi-static, they
are slow enough that the system is always in equilibrium.

We also assume they are reversible:

For a process to be reversible, it must be possible to return
both the system and its surroundings to exactly the same states
they were in before the process began.
 Thermal Processes
Reversible process

The piston is assumed to be frictionless

 Thermal Processes
Quasi-static process is an infinitely slow transition of a system in such a way
that:
• The deviation from thermodynamic equilibrium is infinitesimal.
• All states of the system passes through are equilibrium states.

U = Q - W Q = 0 U = -W
 Thermal Processes
This is an idealised reversible
process.
The gas is compressed; the
temperature is constant, so heat
leaves the gas.
As the gas expands, it draws
heat from the reservoir,
returning the gas and the
reservoir to their initial states.

The piston is assumed to be frictionless.

 Thermal Processes
Work done by an expanding gas, at constant pressure is:
 Thermal Processes: Example
Example:

A gas expands from an initial volume of 0.4 m 3 to a final volume of

0.62 m3 as the pressure increases linearly from 110 kPa to 230 kPa.
Find the work done by the gas.
 Thermal Processes: Example
Answer:

Area1 (rectangle )  Pi (V f  Vi )

Area2 (triangle )   Pf  Pi V f  Vi 

1
2

W  A1  A2  3.7 10 J 4
 Thermal Processes
If the volume stays constant, nothing moves
and no work is done.
 Thermal Processes
If the temperature is constant, the pressure varies inversely with the
volume.
 Thermal Processes
The work done is the area under the curve:
 Thermal Processes
An adiabatic process is
one in which no heat
flows into or out of the
system (Q = 0).
The adiabatic P-V curve
is similar to the
isothermal one, but is
steeper. One way to
ensure that a process is
adiabatic is to insulate
the system.
 Thermal Processes: Example
Example:

A certain gas has an initial

volume and pressure given by
point A in the PV plot. If the gas
is compressed isothermally, its
pressure rises as indicated by the
curve labelled "isotherm.“

If, instead, the gas is compressed adiabatically from point A, does its
pressure follow (a) curve i, (b) curve ii, or (c) curve iii?
 Thermal Processes

• One way to ensure that a process is

adiabatic is to insulate the system.

• Another way is to have the volume

change very quickly. In this case, heat
has no time to flow in or out of the
system.
 Thermal Processes
Here is a summary of the different types of thermal
processes:

At constant pressure, W = PV, Q = U + PV

At constant volume, W = 0, Q= U
Isothermal (constant T), W = Q, U = 0

Adiabatic (no heat flow), W = -U, Q= 0

 Specific Heats for an Ideal Gas: Constant
Pressure, Constant Volume

Specific heats for ideal gases must be quoted either at constant

pressure or at constant volume.

For a constant-volume process,

CV is a specific heat capacity at constant volume

At constant pressure,

CP is a specific heat capacity at constant pressure

 Specific Heats for an Ideal Gas: Constant
Pressure, Constant Volume

Both CV and CP can be calculated for a monatomic ideal gas

using the first law of thermodynamics.
 Specific Heats for an Ideal Gas: Constant
Pressure, Constant Volume
Although this calculation was done for an ideal, monatomic gas, it
works well for real gases.
Specific Heats for an Ideal Gas: Constant
Pressure, Constant Volume
The P-V curve for an adiabatic is given
by:
SECOND LAW OF THERMODYNAMICS
Heat Engine, Heat Pump and Entropy
Second Law of Thermodynamics

Spontaneous flow
of heat from hot to
cold
Second Law of Thermodynamics

Spontaneous rolling of a ball

Second Law of Thermodynamics

Spontaneous
flow of water
 Second Law of Thermodynamics

We observe that heat always flows spontaneously from a warmer

object to a cooler one, although the opposite would not violate
the conservation of energy. This direction of heat flow is one of
the ways of expressing the second law of thermodynamics:
When objects of different temperatures are brought into thermal
contact, the spontaneous flow of heat that results is always from
the high temperature object to the low temperature object.
Spontaneous heat flow never proceeds in the reverse direction (it
is very unlikely to do so).
 Heat Engines and the Carnot Cycle
A heat engine is a device that converts heat into work. A classic
example is the steam engine.

1. Fuel heats the water; the

vapour expands and does
work against the piston
2. The vapour condenses
back into water again and
the cycle repeats
 Heat Engines and the Carnot Cycle

All heat engines have:

• a high-temperature reservoir
• a low-temperature reservoir
• a cyclical engine

These are illustrated schematically here.

 Heat Engines and the Carnot Cycle
An amount of heat Qh is supplied from the hot reservoir to the engine
during each cycle. Of that heat, some appears as work, and the rest, Qc, is
given off as waste heat to the cold reservoir.

The efficiency is the fraction of the heat

supplied to the engine that appears as work.
 Heat Engines and the Carnot Cycle
The efficiency can also be written:

In order for the engine to run, there must be a

temperature difference; otherwise heat will not be
transferred.
 Heat Engines and the Carnot Cycle
The maximum-efficiency heat engine is described in Carnot’s
theorem:
If an engine operating between two constant-
temperature reservoirs (Tc and Th) is to have
maximum efficiency, it must be an engine in which
all processes are reversible.
In addition, all reversible engines operating
between the same two temperatures, Tc and Th, have
the same efficiency.
This is an idealisation; no real engine can be
perfectly reversible.
 Heat Engines and the Carnot Cycle
If the efficiency depends only on the two temperatures, the ratio
of the temperatures must be the same as the ratio of the
transferred heats.
Therefore, the maximum efficiency of a heat engine can be
written:
 Heat Engines and the Carnot Cycle
The maximum work a heat engine can do is then:

If the two reservoirs are at the same temperature, the efficiency is

zero; the smaller the ratio of the cold temperature to the hot
temperature, the closer the efficiency will be to 1.

What if TC is larger than Th?

Can we change the direction of the heat flow?!
Refrigerators, Air Conditioners, and
Heat Pumps
While heat will flow spontaneously only from a higher
temperature to a lower one, it can be made to flow the other
way if work is done on the system.
Refrigerators, air conditioners, and heat pumps all use
work to transfer heat from a cold object to a hot object.
 Refrigerators, Air Conditioners, and
Heat Pumps
We see that the refrigerator is
basically a heat engine running
backwards – it uses work to
extract heat from the cold
reservoir (the inside of the
refrigerator) and releases it into
the kitchen.

Note that Qh= QC + W

- more heat is transferred to the kitchen than is removed from the
refrigerator.
Refrigerators, Air Conditioners, and
Heat Pumps
Coefficient Of Performance :
An ideal refrigerator would remove the most heat from the interior while
requiring the smallest amount of work. This ratio is called the coefficient
of performance, COP.

Typical refrigerators have COP values between 2 and 6. Bigger is

better.
 Refrigerators

                                                                            
Air Conditioner
An air conditioner is essentially
identical to a refrigerator; the cold
reservoir is the interior of the house or
other space being cooled, and the hot
reservoir is outdoors.
Exhausting an air conditioner within
the house will result in the house
becoming warmer, just as keeping the
refrigerator door open will result in the
kitchen becoming warmer.
 Air Conditioner
Low pressure
cold gas
Hot, high pressure

Outside
Inside

liquid

Hot, high pressure

gas

Room temp low

pressure gas
What if we reverse the air condition, outside-inside?
Heat Pump
Finally, a heat pump is the same as
an air conditioner, except with the
reservoirs reversed. Heat is removed
from the cold reservoir outside, and
transferred into the house, keeping it
warm.
Note that the work the pump does
actually contributes to the desired
result (a warmer house) in this case.
 Heat Pump
In an ideal heat pump with two operating temperatures (cold and
hot), the Carnot relationship holds; the work needed to add heat
Qh to a room is:
 Entropy
A reversible engine has the following relation between the heat
transferred and the reservoir temperatures:

Rewriting,

This quantity, Q/T, is the same for both reservoirs, and is defined as the
change in entropy.
Q
The entropy change, S, is defined as: S  in J K .
-1
T
For this definition to be valid, the heat transfer must be reversible. In a reversible
heat engine, it can be shown that the entropy does not change.
Qh QC
 , S  0
Th TC
 Entropy
A real engine will operate at a lower efficiency than a reversible engine;
this means that less heat is converted to work. Therefore,

Any irreversible process results in an increase of entropy.

To generalise:
• The total entropy of the Universe increases whenever a real
irreversible process occurs.
• The total entropy of the Universe is unchanged whenever a
reversible process occurs.

The entropy (increase in disorder) of the Universe

continually increases.
 Order, Disorder and Entropy
If we look at the ultimate fate of the universe in light of
the continual increase in entropy, we might envision a
future in which the entire universe would have come to
the same temperature.
At this point, it would no longer be possible to do any
work, nor would any type of life be possible.
 Third Law of Thermodynamics
Absolute zero is a temperature that an object can get arbitrarily
close to, but never attain. Temperatures as low as 2.0 x 10-8 K
have been achieved in the laboratory, but absolute zero will
remain ever elusive – there is simply nowhere to “put” that last
little bit of energy.

This is the third law of thermodynamics:

It is impossible to lower the temperature of an

object to absolute zero in a finite number of
steps.
 Order, Disorder and Entropy

https://www.youtube.com/watch?v=uQSoaiubuA0&t=53s
 Order, Disorder and Entropy

https://www.youtube.com/watch?v=yKbJ9leUNDE