MODERN Physics

PHY1005
 Module - 1
Thermodynamics
 Introduction
What is thermodynamics?
Thermodynamics in a physics is a branch which deals with the concepts of

Temperature
Heat (Thermal) Energy
Internal Energy (Inter-conversion of heat energy)

and their relation and physical properties of matter.

To be specific, it explains how thermal energy is converted to other form of

energy and how matter is affected by this process.
Thermal energy is the energy that comes from heat. This heat is
generated by the movement of tiny particles within an object.

Thermodynamics is not concerned about how and at what rate these

energy transformations are carried out.

It is based on the initial and final states undergoing the change i.e.,
Thermodynamics is a macroscopic science.

This means that it deals with the bulk system and does not deal with the
molecular constitution of matter.

In 1749, William Thomson coined the term thermodynamics.

The four laws of thermodynamics govern the behavior of these

quantities and provide a quantitative description.
 Important Terms in Thermodynamics
To understand the laws of thermodynamics, you need to make sure you
understand some of the most important terms.

Temperature: Temperature​ is a measure of the average kinetic energy per

molecule in a substance – i.e. how much the molecules are moving around
(in a liquid or gas) or vibrating in place (in a solid). The SI unit for
temperature is Kelvin, where 0 Kelvin is known as “absolute zero”.

Internal energy: it is the total energy of the molecules in a system, meaning

the sum of their kinetic energy and potential energy.

Thermal energy: A difference in temperature between two substances allows

heat to flow, which is the thermal energy​ that transfers from one to the other.
Thermodynamic work: It is mechanical work that is performed making use
of heat energy, like in a heat engine (sometimes called a Carnot engine).

Entropy​: Entropy is a concept that’s difficult to define clearly in words, but

mathematically it’s defined as the

𝑆 = 𝑘 ln 𝑤

𝑘 is Boltzmann constant (​k = 1.381 × 10−23 J K−1) and 𝑤 is the number of

microstates in a system.

In other words, entropy is often referred to as the measure of “disorder” of

the system.

Example: Ice (Solid) Water (liquid) Steam (water vapor)

 Systems and surroundings
The universe is divided into two parts, the system and its surroundings.

The system is the part of universe under thermodynamic consideration.

System: A system is a region containing energy and matter that is

separated from its surroundings by arbitrarily imposed walls or
boundaries. In a thermodynamic analysis, the system is the subject of the
investigation.

Example: water in a beaker, a balloon filled with air, etc.

On the basis of physical properties, systems can be divided into two types.

Homogeneous: The physical state of all its constituents are the same.
Example: a mixture of gases, completely miscible mixture of liquids, …

Heterogeneous: The physical state of all its constituents are not the same.
Example: mixture of oil and water, …

Surrounding: Everything in the universe that is not the part of the system is
called surroundings.

Boundary: Anything which separates the system from its surrounding is

called boundary.

Universe: The system and the surroundings together make up the universe.
 Types of Thermodynamic systems
There are three types of thermodynamic systems are as follows:
➢ Open system
➢ Closed system
➢ Isolated system

Open System: A System which can exchange both

matter and energy with its surrounding is called an
open system.

Example: an open cup of coffee, A steam turbine, …

In this system both energy (heat) and matter (vapor)

is transferred to the surrounding.
Closed System: A system which can exchange only
energy but not matter with its surroundings is
called a closed system.

Here the boundary is sealed but not insulated.

Example: a tightly capped cup of coffee,

Refrigerator, …

In this system energy (heat) is transferred to the

surroundings but no matter (vapor) can escape
from this system.
Isolated System: A system which can exchange
neither matter nor energy with its surroundings
is called an isolated system.

Here boundary is sealed and insulated.

Example: Coffee contained in a thermos flask,

Universe, …

In this isolated system both energy (heat) and

matter (vapor) neither enter nor leave the system.
Properties of the system

The property of the system depends on the mass or the size of the
system is called an extensive property.

Example: Volume, Number of moles, Mass, Internal energy, …

The property of the system is independent of the mass or the size of

the system is called an intensive property.

Example: Refractive index, Surface tension, density, temperature,

Boiling point, Freezing point, molar volume, …
 Thermodynamic Process
The method of operation which can bring to change in the system is called
thermodynamic process.
A system undergoes a thermodynamic process is associated with changes in
pressure, volume and internal energy, …
Example: Heating, cooling, expansion, compression, fusion, vaporization, …
There are four types of thermodynamic process are as follows:
1. Isothermal Process – No change in temperature (𝑑𝑇 = 0).
2. Adiabatic Process – No heat transfer into or out of the system (𝑑𝑄 = 0).
3. Isochoric Process – No change in volume (𝑑𝑉 = 0).
4. Isobaric Process – No change in pressure (𝑑𝑃 = 0).
Isothermal Process: Isothermal process is a change of a thermodynamic
system, in which the temperature remains constant (𝑑𝑇 = 0), during the
change from its initial to final state.

The system exchanges heat with its surrounding and the temperature of the
system remains constant.

For an isothermal process, we follow Boyle’s law (For a fixed mass of gas at a
constant temperature, the volume is inversely proportional to the pressure ).

According to Boyle’s law, the product of pressure and volume (𝑃𝑉) of an ideal
gas is a constant if the gas is kept at isothermal conditions i.e.,

𝑃𝑉 = 𝑛𝑅𝑇 = 𝐶

where 𝑛 is the number of moles of gas present and 𝑅 is the ideal gas constant.
In thermodynamics, the work involved when a gas changes from state A to
state B is simply

For an isothermal process, integral equals the area

under the relevant pressure-volume isothermal curve,
and is indicated in blue in for an ideal gas.

Substitute, 𝑃 = 𝑛𝑅𝑇 / 𝑉, we have

In an isothermal process only temperature remains constant i.e., 𝑑𝑇 = 0 but

the change in heat will never equal to zero i.e., 𝑑𝑄 ≠ 0
Example: thermo-flask, refrigerator…
Adiabatic Process : An adiabatic process is a thermodynamic process in which there
is no heat transfer into or out of the system (𝑑𝑄 = 0).

The system can be considered to be perfectly insulated. In an adiabatic process if

➢ work is done by the system its temperature decreases

➢ work is done on the system its temperature increases

because, the system cannot exchange heat with its surroundings.

According to the first law of thermodynamics : 𝒅𝑸 = 𝒅𝑼 + 𝒅𝑾
for an adiabatic process, 𝒅𝑸 = 𝟎 i.e., 𝒅𝑼 = −𝒅𝑾

For adiabatic expansion, 𝒅𝑾 is +𝒗𝒆 and internal energy 𝒅𝑼 is −𝒗𝒆 i.e., when work is
done by the system adiabatically its internal energy is decreasing

For adiabatic compression, 𝒅𝑾 is −𝒗𝒆 and internal energy 𝒅𝑼 is +𝒗𝒆 i.e., when work
is done on the system adiabatically its internal energy is increasing
 For an adiabatic process, we follow Poisson’s law i.e.,

For an adiabatic process, the work done by the system is given by

where 𝑛 is the number of moles of gas present and 𝑅 is gas constant and 𝑐𝑝
and 𝑐𝑣 are specific heat at constant pressure and volume.
Isobaric Process : The pressure (𝑃) is constant in this process, the volume of the
system changes.

The work (𝑊) done can be calculated as 𝑊 = 𝑃 𝑉𝑓 − 𝑉𝑖 = 𝑃∆𝑉.

If ΔV is +𝑣𝑒 (expansion), the work done is positive.

If ΔV is −𝑣𝑒 (contraction), the work done is negative.

Isochoric Process : The volume remains constant in an isochoric process.

The system does not do any work (since Δ𝑉 = 0 then 𝑊 = 𝑃 𝑑𝑉 is also zero).

Such a process can be achieved by placing a thermodynamic system in a closed

container which neither contracts nor expands.

Thus, from the first law of thermodynamics (𝑄 = Δ𝑈 + 𝑊), change in internal

energy becomes equal to the heat transferred (Δ𝑈 = 𝑄) for an isochoric process.
 Difference Between Isothermal and Adiabatic Process

Isothermal process Adiabatic process

An adiabatic process is in which occur
An isothermal process is in which occur
without any heat transfer between the
at a constant temperature
system and the surrounding
Work done is due to the change in the Work done is due to the change in its
net heat content in the system internal energy
The temperature cannot be varied The temperature can be varied

There is a transfer of heat There is no transfer of heat

Reversible process : The process in which the
system and surrounding can be restored to the
initial state from the final state without changes
in the thermodynamic properties of the universe
This ice cream can be
is called a reversible process. converted to liquid on
heating, and again it can be
There are two important conditions for the converted to ice cream on
reversible process to occur. freezing.

Firstly, the process should occur infinitesimally

slowly
Water can be converted to
Secondly throughout the process, the system and ice on freezing. And this ice
surroundings must be in equilibrium with each can be again converted back
other. to water on heating.
Irreversible process : The process in which
the system and surrounding cannot be
restored to the initial state from the final
This wood can be converted to fire,
state is called an irreversible process. but fire can not be again converted
to wood.

All the processes occurring in nature are

irreversible processes.
During the irreversible process the system
and surroundings are not in equilibrium
Egg can be fried on applying heat.
with each other. But fried egg can not be converted
to original egg on cooling it.
 Concept of Heat capacity
Just see the picture.
Sand is receiving same amount of heat (heat energy)
from the sun
Water of the ocean is also receiving the same amount of
heat from the sun.
Then why is there a difference in the temperature of sand and water?
What this happens?
Sand gets heated more as compared to water. We can say that, for heating the sand,
only a few amount of heat is required. While for heating the water, a lot of heat is
required.
In other words, sand is not having more capacity to absorb heat. While water keeps on
absorbing the heat of the sun.
Heat capacity is something similar to this.

The amount of heat required for the same change in

temperature, is different for different objects

For example, take 1 kg of sand and it is at 20 °C. Now I

want to increase its temperature to 25 °C using a burner.

Amount of heat required to increase this temperature

from 20 °C to 25 °C is say 1000 Joules.

Now, take the same 1 kg of water in this bowl at 20 °C and increase its temperature to
25 °C using a burner.

Guess what will happen? Water will consume more heat energy compared to the
same quantity of sand.

This happens because water has more capacity to absorb the heat.
Heat capacity 𝑯𝒄 : The ratio of heat supplied (𝑸) to the system to the
change in it’s temperature ∆T is called heat capacity of that system.
Or
Heat capacity 𝑯𝒄 is defined as the amount of heat absorbed (𝑸) in order
to increase the temperature (∆𝑻) by 1 unit.

𝑄
The heat capacity 𝐻𝑐 = ൗ∆𝑇 . The unit of heat capacity is J/K

From the above explanation, that heat capacity depends on the material of the
system.
Heat capacity also depends on the mass of the object.

Bigger the mass of the object, the more heat will be absorbed, so it’s heat capacity will
be more. While smaller the mass of the object, less heat will be absorbed, so it’s heat
capacity will be less.
 Specific heat capacity
Specific heat capacity ( 𝑪 ): Specific heat
capacity (𝑪) is defined as the amount of
heat absorbed (𝑸) in order to increase the
temperature ( ∆𝑻 ) by 1 unit, of a unit
mass(𝒎).
𝑄ൗ
𝐶 = 𝑚 ∆𝑇

The unit of specific heat capacity is J/kg K.

The specific heat capacity of water is 4182 J/kg K.

Specific Heat at Constant Volume (𝒄𝒗)

Specific heat at constant volume is the change of specific internal energy with
respect to temperature when the volume is held constant (Isochoric process).

𝑑𝑈
𝑐𝑣 =
𝑑𝑇 𝑣

Specific Heat at Constant Pressure (𝒄𝑷)

Specific heat at constant pressure is the change of specific enthalpy with respect to
temperature when the pressure is held constant (Isobaric process).

𝑑𝑈
𝑐𝑃 =
𝑑𝑇 𝑃
 zeroth law of thermodynamics
In 1935, Ralph H Fowler discovered the title “Zeroth law of thermodynamics”.

Fowler came upon one text – “every physical quantity must be measurable in
numeric term”.

There was no discovery of any term like “temperature” before 1935.

And main thing all three laws of thermodynamics were already discovered before
1935 without defining temperature.

Fowler realized that thermal equilibrium is very important phenomenon and it gives
the definition of “temperature”.

According to Fowler, this law should be kept first for proper understanding of
thermodynamics laws.
But already so many books were published with the first, second and third laws.
So changing the numbers of these laws can create a lot of confusion. Thus he was
forced to adopt the number “zero” for his law. And finally this law was named
“zeroth law of thermodynamics”.

Zeroth law of thermodynamics : “If two bodies A and B are in thermal

equilibrium with third body C, then body A and B are also in thermal
equilibrium with each other”.

From zeroth law of thermodynamics we found that there is one physical property
which indicates whether the “temperature” of the bodies are same, then the bodies
are in thermal equilibrium with each other.
Application of zeroth law of thermodynamics: i) To measure human body
temperature and atmospheric temperature. Ii) Temperature measurement in air
conditioners. iii) Temperature measurement in refrigerator, iv) food processing
industries
 How will you define temperature?
The kinetic energy is more, then the body is warm (or hot) and if kinetic energy is
less, then the body will be cold.

Thus, the definition of the temperature are as follows:

“Temperature is a measurement of the average kinetic energy of the

molecules in any object”.

“Temperature can also be defined as a degree of hotness or coldness

of an object”.
 First law of thermodynamics
First law of thermodynamics: “ The net change in internal
energy of a system (∆𝑼) is equal to the heat added to the system
(𝑸) minus work done by the system (𝑾)”.
I know this is little bit complicated to understand.
I’ll explain you with an example.

𝑼𝟐
𝑼𝟏

This boy takes the energy He has gained 𝑸 amount of He spends some W amount of
drink and he gains 𝑸 amount energy and he is ready to do energy in doing work, After
of energy from it. We can say work. And right now, he is doing this work, his internal
that 𝑸 amount of energy is having internal energy 𝑼𝟏. energy becomes 𝑼𝟐.
entering the body.
Now here,
𝑄 = Heat energy added to the system
𝑊 = Energy in the form of work
𝑈1 = Internal energy of the system in initial state
𝑈2 = Internal energy of the system in final state

Thus, this change in internal energy is nothing but ∆U = 𝑈2 − 𝑈1 .

Above statement can be mathematically written as ∆𝑈 = 𝑈2 − 𝑈1 = 𝑄 – 𝑊

This equation is known as the first law of thermodynamics

This internal energy ∆U is nothing but a sum of kinetic energy, potential energy and other
energies present in the molecules of the system.

Kinetic energy: Kinetic energy is the energy which an object possesses due to its
motion.

Potential energy: Potential energy is the energy stored in a body due to its
position with respect to some other body.
 Work
What is work? How is it related to first law of thermodynamics?

Because it is very important for you to know about work for understanding the
applications of the first law of thermodynamics.

When can we say that work is done?

When a force is applied to any body and if that body moves in the direction of
applied force, then we can say that work is done.

During the thermodynamics process, the volume of the system may increase or
decrease.

But how will you decide that the thermodynamic system is doing work on the
surrounding or surrounding is doing work on the system.
Who is doing work on whom?
let’s consider a piston cylinder assembly as
shown in the figure.

When heat is supplied to the system, then

its volume increases.
Let;
𝑉1 = initial volume of the system
𝑉2 = final volume of the system

The pressure of the system remains constant because, as heat is supplied, the
volume increases and thus the pressure remains constant inside the system.

The work done by the system can be obtained from following formula

𝑊 = 𝑃 (𝑉2 − 𝑉1 ) = 𝑃 ∆𝑉
What should be the sign of this work done?

When the volume of the system When the volume of the system
increases, then we have to take decreases, then we have to take
sign of work 𝑊 as +𝑣𝑒. This is a sign of work 𝑊 as −𝑣𝑒. This is a
work done by the system. work done on the system.
Work done in Isothermal and adiabatic expansion.
Refer Slide no 14-17
 Second law of thermodynamics
The laws of thermodynamics describe the relationships between thermal energy, or
heat, and other forms of energy, and how energy affects matter.

The First Law of Thermodynamics states that the total quantity of energy in the
universe stays the same i.e., the total internal energy of the system is conserved

The limitation of 1st law of thermodynamics, the second law of thermodynamics was
discovered.

What is the limitation of first law of thermodynamics?

The limitation of the 1st law of thermodynamics can be explained the following
example.

We take hot cup of coffee and which is keep in the room, then it will cool down after
few minutes. This process occurs on it’s own (spontaneous).
 But what about the reverse process?
Will the reverse process occur on it’s own?
Will the heat of the room be transferred
back to the cup of coffee?

According to the first law of thermodynamics, the heat energy of the room can be
transferred back to the coffee.

But in actual practice it is not possible to have such a process taking place on it’s
own.

This is only the limitation of first law of thermodynamics, that it does not describe
the direction of the process.
In our example, the first law fails to say whether the spontaneous heat transfer takes
place from coffee to the room or from room to the coffee?

The limitation of 1st law of thermodynamics, the second law of thermodynamics was
discovered.
The Second Law of Thermodynamics is about the quality of energy.

It states that as energy is transferred or transformed, more and more of it is wasted.

The second law of thermodynamics is very confusing because it has many statements.

The second law of thermodynamics will be explained with suitable examples.

Example - 1

If remove this white separator, then both the But what about the reverse process? It is
gases will get mixed with each other on it’s possible to separate both the gases by
own (spontaneous). putting the separator? No, it is not possible.
Example - 2
From these two examples, second law of
thermodynamics is all about this only.

❑ Two gas will get mixed (If they are allowed to mix in
the same container) by it’s own (spontaneous).

The hot coffee will lose its ❑ Hot coffee becomes cold (Heat flow taking place from
heat on its own without any
external help. higher temperature body to lower temperature body)
on it’s own (spontaneous).

All these processes take place on it’s own and they also
occur in a particular direction.

what about the reverse Now the second law of thermodynamics tells us the
process? Will this coffee direction in which the process (spontaneous or not) will
absorb heat on its own? No, occur.
it won’t.
The second law of thermodynamics can be stated in three ways.

➢ Second law of thermodynamics for heat engine (Kelvin Planck’s statement)

➢ Second law of thermodynamics for heat pump/refrigerator (Clausius’s statement)

➢ Second law of thermodynamics based on entropy

𝟐𝒏𝒅 law of thermodynamics for heat engine

(Kelvin Planck’s statement)

Kelvin Planck’s statement : – “A heat engine must exchange the heat with at least
two thermal reservoirs, one at higher temperature and other at lower temperature,
then only the engine will operate”.
Or
“Perfect engine with 100% efficiency is impossible”
Heat engine is continuously taking heat from the heat
source and converting this heat into equal amount of
work.

This process is valid according to the first law (one form of

energy can be converted to another form of energy) of
thermodynamics.

According to the Kelvin Planck’s statement of second law of thermodynamics, this

type of heat engine is not possible. It has a single heat source.

That is, there is no lower temperature source.

So heat transfer cannot take place in this case. Thus, this heat can not be converted to
work without any heat transfer.

Kelvin Planck’s statement says that there must be at least two thermal reservoirs to
operate the engine.
This type of heat engine (see figure) is possible
according to the Kelvin Planck’s statement of
second law of thermodynamics.

It is operating between two temperature reservoirs

one at a higher temperature and other at a lower
temperature.

This heat engine will give efficiency less than 100%.

Thus, this heat engine obeys first law as well as second law of thermodynamics.

Kelvin Planck’s statement of second law of thermodynamics explain the thermal process taking
spontaneously (by it’s own). Then the process is called spontaneous process.
 𝒏𝒅
𝟐 law of thermodynamics for heat pump/refrigerator
(Clausius’s statement)

Clausius’s statement : - “It is impossible to construct a device (heat

pump/refrigerator) that can transfer heat from cold body to the hot body
without absorbing any work.”
(OR)
“Heat always flows from higher temperature body to lower temperature
body. It’s reverse flow does not take place on its own.”
 Consider a heat pump as shown in the figure (Left).

This heat pump absorbs heat from the lower temperature body and
rejects heat to the higher temperature body without supply of any
work. Which is obey first law of thermodynamics.

But such a device can not transfer heat from lower temperature
body to higher temperature body without any supply of work to it.

So according to Clausius’s statement of second law of

thermodynamics, this type of heat pump is not possible.
Now see the figure (Right). This type of heat pump is possible
according to the Clausius’s statement of second law of
thermodynamics.

It is consuming some work in order to transfer heat from lower

temperature body to higher temperature body.

Thus, this heat pump obeys 1st law as well as 2nd law of
thermodynamics.

This system is operating with the help of external work. Then this
process is called driven process.
 Second law of thermodynamics
(Entropy)
Before starting the 2nd law of thermodynamics based on entropy, we need to
understand the two terms

1. Randomness
2. Entropy
1. Randomness
The movement of atoms or molecules is known as randomness.

Now we consider three states of systems like solid, liquid and gas.

Solids show less movement of atoms because the molecules are arranged
periodically with the strong bonding force between the neighboring molecules.

Then the randomness effect of the solid is minimized.

Molecules in the liquids have more movement due to the strength of bonding
force between the molecules is decreasing.

Then the molecules are freely moving than solids.

In gases show maximum movement of molecules than liquids as shown in the

figure.

The strength of bonding force between the molecules is negligible then the
molecules are more freely moving in gases compare to liquids

Thus we can say that solids have less randomness, liquids have more
randomness compared to solids and gases have maximum randomness.

The movement of atoms or molecules is known as randomness.

 2. Entropy
The measurement of randomness of the system is known as Entropy.
(OR)
Entropy is the measurement of disorder of the system.

It is just a measurement of how much randomly the molecules are moving in

a system.

❖ In solids, the molecules are properly arranged, that means it has less randomness,
so entropy of solids is least.

❖ In gases, the molecules move very fast throughout the container. It has more
randomness which means it has more entropy.

❖ The entropy of liquids lies in between the solids and liquids

The formula for a change in entropy is given by;

∆𝑺 = ∆𝑸/𝑻

Entropy statement of Second law of thermodynamics

“In all the spontaneous processes, the entropy of the universe increases.”

∆𝑺𝑼𝒏𝒊𝒗𝒆𝒓𝒔𝒆 > 𝟎

∆𝑺𝑼𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = ∆𝑺𝒔𝒚𝒔𝒕𝒆𝒎 + ∆𝑺𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈 > 𝟎

∆𝑸𝒔𝒚𝒔𝒕𝒆𝒎 ∆𝑸𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈
∆𝑺𝑼𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = + >𝟎
𝑻𝒔𝒚𝒔𝒕𝒆𝒎 𝑻𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈
 Examples of 𝟐𝒏𝒅 law of thermodynamics
1. Cars and bikes engine

2. Refrigerator using electricity to change the direction of heat flow

3. Ice kept on a table will melt on it’s own

4. Hot coffee becomes cold on it’s own

5. Air leaks from the balloon

6. Gases will mix automatically on it’s own

7. Water always flows from higher level to lower level

8. A gas takes the entire volume of a container

 Heat engine
How does this engine work?

It works with the help of fuel.

The fuel burns inside the engine and produces heat.

This heat is used to do some useful work.

We can explain the working principle of heat engine

with a simple diagram.

In figure shows two bodies, hot body and a cold body.

According to Kelvin Planck’s statement of second law of thermodynamics, heat transfer always
takes place from hot body to cold body.

So here also heat will flow from hot body to cold body.
Let, 𝑄1 = Heat transferred from the hot body
𝑄2 = Heat received by the cold body.
Now, if we keep the engine between this hot and cold bodies, then work can be
produced from this engine as heat flows from the hot body to the cold body.

Here, the total amount of work done by this heat engine will be;
𝑊 = 𝑄1 – 𝑄2
The unit of work done is the same as the unit of heat, i.e Joule (J).

The thermal efficiency of heat engine is the ratio of net output work (𝑊) to the heat
supplied (𝑄1) to the engine.
The thermal efficiency of a heat engine is given by the following equation.
𝜂 = 𝑊/𝑄1
Heat engine is a machine or a device which converts heat energy into mechanical
energy (work) by transfer of heat from high temperature to lower temperature
 Heat pump
Heat engine we knew that heat transfer takes place from
𝑇1
higher temperature body to the lower temperature body
and the device or machine produces some useful work.
𝑊 = 𝑄1 − 𝑄2

But what if we want to transfer the heat in the reverse

direction? i.e from lower temperature body to higher 𝑇2
temperature body.

Heat transfer never takes place from lower temperature to higher temperature on it’s
own.

In this case a new device is used to do so, and this device is known as a heat pump.

As shown in above diagram, heat pump extracts 𝑄2 amount of heat from cold body
and delivers 𝑄1 amount of heat to the hot body.
We need to supply some work to this device in order to transfer the heat from lower
temperature to higher temperature.
The amount of input work required is;
𝑊 = 𝑄1 − 𝑄2
In heat pumps and refrigerators, the term efficiency is replaced by Coefficient of performance
(COP). COP is defined as a ratio of heat delivered to hot body (𝑄1 ) to the work input (𝑊) to the
system.
𝐶𝑂𝑃 = 𝑄1 /𝑊
Heat pump: “Heat pump is a device which is used to transfer heat from lower temperature to
higher temperature by using some input work”.

𝐶𝑜𝑜𝑙𝑖𝑛𝑔 𝐸𝑓𝑓𝑒𝑐𝑡 𝑄2 𝑇2
For Carnot refrigerators 𝐶𝑂𝑃 = = =
𝑊𝑜𝑘𝑟 𝑖𝑛𝑝𝑢𝑡 𝑊 𝑇1 − 𝑇2
𝐻𝑒𝑎𝑡𝑖𝑛𝑔 𝐸𝑓𝑓𝑒𝑐𝑡 𝑄1 𝑇1
For Carnot Heat pump 𝐶𝑂𝑃 = = =
𝑊𝑜𝑘𝑟 𝑖𝑛𝑝𝑢𝑡 𝑊 𝑇1 − 𝑇2

𝑄1 = 𝑊 + 𝑄2
 Carnot engine
A heat engine that works according to the Carnot cycle is known as a Carnot engine.
The Carnot engine, as proposed by Nicolas Léonard Sadi Carnot in 1824, is the one
that operates on reversible thermodynamics. It has been named after its invention by
Carnot.

Carnot engine is a reversible engine that operates between two temperatures 𝑇1

(source) and 𝑇2 (sink).
It is an analytical engine that gives the maximum efficiency that a heat engine can
have while between two working reservoirs (temperatures).
It is in the process of conversion of heat into work and conversely.

Carnot Theorem : “The systems working between the two temperatures T1 (hot
reservoir - Source) and T2 (cold reservoir - Sink), cannot have more efficiency than
the Carnot engine that is working between the same two reservoirs”.
 Components of Carnot Engine
The efficiency of this engine depends on the temperature of the hot and cold
reservoirs and is independent of the nature of the working substance.

The Carnot engine has the following major components:

1. Insulating Stand
2. Source (Hot reservoir)
3. Sink (Cold reservoir)
4. Cylinder with working medium

1. Insulating Stand
An insulating stand uses to operate an
adiabatic operation.

This part of the Carnot engine is made of

non-conducting material.

there is no heat transfer through this stand.

2. Source (Hot reservoir)

A source is a hot body that operates at a constant temperature 𝑇1 .

It delivers heat to the system for working.

This source has unlimited heat volume.

At a constant temperature (𝑇1 ), you can withdraw heat from it according to your wish.

The temperature of the heat source remains constant even after extracting large heat.
3. Sink (Cold reservoir)

It is a low-temperature body that has a constant low temperature (𝑇2 ).

The sink also has unlimited heat capacity.

This means the heat supplied to a sink does not raise its temperature.
4. Cylinder with a working medium

The cylinder has a conductive base and heat transfer

takes place through this base of the cylinder.

A cylinder is having non conducting walls (insulated

walls) through which no heat transfer takes place.

It is equipped with a completely frictionless and

non-conductive piston.

This piston moves up and down for gas

compression.

In the Carnot engine, an ideal gas uses as the

working medium.
 Carnot Cycle

The Carnot cycle is an ideal reversible

closed thermodynamic cycle, which
involves four stages of
operations. The stages are: 𝑇1

❑ Isothermal expansion
❑ Adiabatic expansion
❑ Isothermal compression 𝑇2 ↑ 𝑇1
𝑄1
❑ Adiabatic compression
𝑄2 𝑇1
↓ 𝑇2

𝑇2
1. Isothermal expansion
PV=nRT
The gas is placed in thermal contact with a heat
reservoir (source) at a temperature 𝑇1 .

The gas absorbs heat 𝑄1 from the heat reservoir

and is allowed to expand isothermally, doing
work 𝑊1 .

Internal energy 𝐸𝑖𝑛𝑡 of an ideal gas is a function of the temperature only.

The change of the internal energy is zero, i.e., ∆𝐸𝑖𝑛𝑡 = 0 during this isothermal
expansion.

From the first law of thermodynamics, ∆𝐸𝑖𝑛𝑡 = 𝑄 − 𝑊 = 𝑄1 − 𝑊1 = 0 , then the

amount of heat absorbed by the gas is equal to work done by the system i.e., 𝑄1 = 𝑊1 .

𝑉2
Work done by the gas is 𝑊1 = 𝑛𝑅𝑇1 ln 1
𝑉1
2. Adiabatic expansion
The gas is thermally isolated from both the hot
and cold reservoirs.

Thus gas can neither gain nor lose heat, so it

called an 'adiabatic' process.
The gas rises to expand by the drop in pressure, doing work is 𝑊2 .
The gas begins to expansion without heat input causes it to cool i.e., temperature
𝑇1 ↓ 𝑇2 here 𝑇2 < 𝑇1 .

From 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 and the equation of state for an ideal gas, 𝑃𝑉 = 𝑛𝑅𝑇, we have

𝑃𝑉 𝛾 = 𝑃𝑉𝑉 𝛾−1 = 𝑛𝑅𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡e Work done by the gas is

∴ 𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑛𝑅
𝑊2 = 𝑇1 − 𝑇2 3
𝑠𝑜 𝑡ℎ𝑎𝑡 𝑇1 𝑉2 𝛾−1
= 𝑇2 𝑉3 𝛾−1 2 𝛾−1
3. Isothermal compression

The gas is placed in thermal contact with a

cold reservoir at temperature 𝑇2 and
compressed isothermally.

During this process, surroundings do

work (𝑊3 ) on the gas by pushing the piston
down, causing amount of heat energy 𝑄2
leave to a cold reservoir (sink).

From the first law of thermodynamics, ∆𝐸𝑖𝑛𝑡 = 𝑄 + 𝑊 = 𝑄3 + 𝑊3 = 0, then the amount of heat
delivered by the gas is equal to work done on the system i.e., 𝑄3 = − 𝑊3

Work done on the gas is

𝑉4 𝑉3
𝑊3 = 𝑛𝑅𝑇2 ln = −𝑛𝑅𝑇2 ln 4 ℎ𝑒𝑟𝑒 𝑉3 > 𝑉4
𝑉3 𝑉4
4. Adiabatic compression

The gas is thermally isolated and returned to

its initial state by adiabatic compression.

In this process, work 𝑊4 is done on the gas.

The temperature of the gas rises i.e., 𝑇2 ↑ 𝑇1

here 𝑇2 < 𝑇1 in the process of adiabatic
compression.

𝛾−1 Work done by the gas is

∴ 𝑇𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑛𝑅
𝑠𝑜 𝑡ℎ𝑎𝑡 𝑇2 𝑉4 𝛾−1
= 𝑇1 𝑉1 𝛾−1 𝑊4 = − 𝑇1 − 𝑇2 6
5 𝛾−1
 efficiency of Carnot engine
The total work done by the gas in the one complete Carnot cycle is given by
𝑊 = 𝑊1 + 𝑊2 + 𝑊3 + 𝑊4

Herev 𝑊1 = 𝑄1 , 𝑊2 = −𝑊4 , and 𝑊3 = −𝑄2 then

𝑊 = 𝑄1 − 𝑄2
Net efficiency of Carnot engine for one complete cycle is

𝑁𝑒𝑡 𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑡ℎ𝑒 𝑔𝑎𝑠 𝑊 𝑄1 − 𝑄2 𝑄2

𝑁𝑒𝑡 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝜂 = = = =1−
𝐻𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑔𝑎𝑠 𝑄1 𝑄1 𝑄1

Substitute eqn. (1) and eqn. (4) in the above equation, the net efficiency of Carnot engine is
𝑉3 𝑉3
𝑄2 𝑛𝑅𝑇2 ln 𝑇2 ln
𝑉4 𝑉4
𝑁𝑒𝑡 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝜂 = 1 −
𝑄1
=1−
𝑉2
=1−
𝑉2 7
𝑛𝑅𝑇1 ln 𝑇1 ln
𝑉1 𝑉1
 𝛾−1 𝛾−1
From equation of adiabatic expansion 𝑇1 𝑉2 = 𝑇2 𝑉3
1
𝑉2 𝑇2 𝛾−1
= 8
𝑉3 𝑇1
𝛾−1 𝛾−1
From equation of adiabatic compression 𝑇2 𝑉4 = 𝑇1 𝑉1
1
𝑉1 𝑇2 𝛾−1

𝑉4
=
𝑇1
9

RHS of equations (8) and (9) are equal, then LHS are also equal, therefore
𝑉2 𝑉1 𝑉2 𝑉3
= ⇒ = 10
𝑉3 𝑉4 𝑉1 𝑉4
Substitute eqn. (10) in eqn. (7)

𝑊 𝑄2 𝑇2
𝑁𝑒𝑡 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝜂 =
𝑄1
=1−
𝑄1
=1−
𝑇1
11
Why isn’t the Carnot cycle used in practical applications?

In a Carnot heat engine, the ideal gas uses as a working medium

trapped in a cylinder.

The boundaries of this cylinder are fully isolated.

A Carnot cycle works in the following four processes:

1. Isothermal expansion
2. Adiabatic expansion
3. Isothermal compression
4. Adiabatic compression.

From the above four processes, two are reversible isothermal, and
two are adiabatic processes.
The Carnot cycle can’t use in practical applications due to the
following reasons:

❑ The isothermal process is very slow, while the adiabatic is a

very fast process. In reality, a fast and a slow
process can’t operate at the same time.

❑ Carnot’s cycle says that a heat engine can achieve 100%

efficiency. This 100% is only possible if the temperature of the
sink (cold reservoir) is at absolute zero, but theoretically and
practically, this is not possible.

Due to the above reasons, the Carnot cycle can’t use with practical
applications.
 Limitations of Carnot Cycle

The Carnot cycle has the following limitations:

➢ It is an ideal cycle. In other words, the Carnot cycle doesn’t exist and cannot be
constructed. Therefore, the Carnot cycle is only a theoretical concept.

➢ According to thermodynamics, in an isothermal process, the temperature doesn’t

change, while the Carnot cycle says that there will be the addition of heat during
isothermal expansion, which is impossible.

➢ The Carnot cycle only explains to heat engine while it doesn’t explain other types
of equipment.

➢ Heat loss can occur in a real engine while the Carnot cycle has oppositive
working.
Application of Carnot Cycle

Carnot Cycle is used in the various fields like

❖ thermal devices
❖ heat pumps
❖ refrigerators
❖ steam turbines
❖ Combustion engine
❖ Reaction turbines of airplane
 Third law of thermodynamics

When German chemist Walther Hermann Nernst studied about the second law of
thermodynamics, his mind was completely disturbed.

He studied that the entropy of the universe keeps on increasing for all the process occurring on
it’s own.

He thought that, the entropy of the universe will not increase and it will remain constant.

Then he studied everything about entropy. After a lot of studying and research work, he
discovered the third law of thermodynamics.

“The value of entropy of a completely pure crystalline substance is zero at absolute

zero temperature”
What is absolute zero temperature? Is it possible to achieve practically?

Absolute zero temperature is the coldest possible temperature in the universe ( 0 K or -273 o C)

Absolute zero is so much cold temperature that all the atoms and molecules of a substance gets
freezed up.

The atoms and molecules of any substance will not be able to move, vibrate or oscillate inside
the substance.

Even gases like hydrogen, helium, oxygen get freezed up and become solids at this temperature.

According to second law of thermodynamics, heat will move from the hot body to a colder body.

So if we try to cool down the object to absolute zero, then that object will keep on receiving heat
from the surrounding and so it’s just a theoretical concept.

Thus absolute zero temperature is practically not possible.

Why are we studying the third law of thermodynamics?
Once we have studied the third law, you can easily find the absolute entropy of any substance
at a given temperature. Explanation as follows
Compare the entropy of a given substance at temperature T with the entropy of that substance
at zero Kelvin temperature.
We have to calculate the change in entropy between these temperatures.
𝑆𝑇 − 𝑆0 = ∆𝑆

The change in entropy (∆S ), using the formula. 𝒄𝒑 is the specific heat capacity
𝑻𝒄
𝒑
𝚫𝑺 = 𝑆𝑇 − 𝑆0 = න 𝒅𝑻 at constant pressure
𝟎 𝑻
We know that at 0 K temperature, the entropy will be zero i.e.,𝑆0 = 0.
Thus the absolute entropy of any substance at a given temperature T is
𝑻𝒄
𝒑
𝚫𝑺 = 𝑺𝑻 = න 𝒅𝑻 = 𝒄𝒑 ln 𝑻 = 𝒄𝒑 𝟐. 𝟑𝟎𝟑 log 𝟏𝟎 𝑻
𝟎 𝑻
Let us consider a hot cup of coffee of temperature 55𝑜 𝐶. The temperature of the
surrounding is 23𝑜 𝐶 . Calculate the entropy of the universe if surrounding is
transferred 13 J of energy to the cup of coffee.

𝑜
Let us consider a hot cup of coffee of temperature 55 𝐶. The temperature of the
surrounding is 23𝑜 𝐶. Calculate the entropy of the universe if cup of coffee lose 13 J of
energy to surrounding.