More Sir’s Physics Notes

Written By : Mr. A.V.More

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 More Sir’s Physics Notes

Thermodynamics
Thermodynamics :
The branch of physics which deals with the study of heat and temperature and the inter conversion of
heat and other forms of energy is called as Thermodynamics.
System : -
A part of universe which is under thermodynamics study is called as system.
Surrounding (Environment) :-
The remaining part of the universe other than the system is called as surrounding or environment.
Boundary :-
A line which separate system from surrounding is called as boundary.
Types of system
1) Open system :
A system in which , there is exchange of energy as well as matter with the surrounding is called
as open system.
Example : - 1) Thermos flask is an example of isolated system
2) Cup of tea placed on table
2) Closed system :- A system in which there is a exchange of energy not a matter with surrounding is
called as closed system.
Example :- 1) Water boiling in a boiler is an example of closed system
2) Isolated system :- A system in which there is no exchange of energy as well as matter with
surrounding is called as isolated system.
Example :- Thermal flask is an example of isolated system.
Thermodynamics process : -
A process in which a thermodynamics state of system is changed is called as thermodynamic
process.
There are different type of process
1) Isothermal process: - A process in which temperature of system remain constant is called as
isothermal process.
= constant
Example :- Melting point of ice which takes place at constant temperature in an isothermal process.
2) Isobaric process : -
A process in which pressure of system remains constant is called as isobaric process .
= constant
Example : - Boiling of water at constant pressure.
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3) Isochoric process : - A process in which volume of a system remains constant is called as isochoric
process.
= constant
Example :- Heating of gas in a constant volume container.
4) Adiabatic process : - A process in which there is no exchange of heat between system and
surrounding is called as adiabatic process.
i.e . Q = 0
Example :- 1) A tire is an example of adiabatic process 2) A balloon
5) Cyclic process : - A thermodynamic process that returns a system to its in initial state is called as
cyclic process.
In this process the initial and final state is same.
Thermodynamic equilibrium: -
A system is said to be in thermodynamic equilibrium ,if its microscopic properties like pressure,
temperature, volume and concentration do not change with time.
There are three types of equilibrium : -
1) Thermal equilibrium : -
The system is said to be in thermal equilibrium if its temperature of the system remains constant.
2) Chemical equilibrium : -
The system is said to be in chemical equilibrium if its chemical composition of the system remains
constant
3) Mechanical equilibrium :-
It is the equilibrium where no work is done on the system or no work is done by the system.

Heat :
 Heat is a form of energy.
 It is always flow from higher temperature to lower temperature ,
 The flow will stop when the temperature of both the bodies will same.
 Then the two bodies are in thermal equilibrium.

Temperature : -
It measures hotness of the body.
It determine the direction of flow of heat when two bodies are placed in thermal contact.

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Internal energy : -
The sum of molecular Kinetic energy and potential energy of all molecules present in the system is
called as internal energy .
 All molecules are in random motion.
 The energy associate with the random motion, the disordered motion of the molecules of the
system is called as internal energy.
 It is donated by ‘U’
 It’s value depends only on the given state of system and not on the path.
 For an ideal monoatomic gas such as argon, the internal energy is just the transnational kinetic
energy of atoms having a linear motion.
 For a polyatomic gas , such as carbon dioxide we consider the rotational and vibrational kinetic
energy in addition to their transnational kinetic energy
 In case of liquid and solid , potential energy of molecules due to intermolecular attractive forces
between them.
 It is directly proportional to absolute temperature.
 It is a state function, it means it's value depends upon initial and final state of system and not upon
the path.
 It is an extensive property.
 It's absolute value cannot be measured but change in internal energy can be calculated when
system changes from one state to another
i.e. U = U2 – U1

Thermodynamic property : -
Extensive property : -
The property whose value depends upon the quantity of matter present in the system is called as
extensive property.
Example : - internal energy, mass, weight, energy area, volume, enthalpy.
Intensive property : -
The property which value does not depends upon the quantity of matter present in the system is called
as intensive property
Example : - Temperature, pressure, density, surface tension, viscosity, melting point ,Boiling point,
Refractive index, molar heat capacity.
Heat is depend upon quantity of motion present in system.
Heat is extensive property where temperature is intensive property.
Quasi static process :
The thermodynamic process which is infinitely slowly is called as quasi static process.

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Explain how internal energy of system is changed by heating ?
Consider a cylinder having movable, massless and frictionless
piston at its one end

Ts - be the temperature of the system

TE - be the temperature of the environment
Case : I
Let TE is greater than Ts
The cylinder can be brought in contact with source of heat such
as burner as shown in figure.
Due to temperature difference between the source of heat ( environment ) and the system with cause
flow of heat towards a gas in cylinder .
There will be an increasing in the energy of gas
Case II: Let the temperature of surrounding (environment ) is lower than gas .
The gas losses heat energy to the surrounding and cool down
Que: How internal energy of system is changed by doing work ?
If the piston is pushed inside the gas, so that gas is
compressed .
In this case, the piston does some work on the gas in
moving it through a some distance, the gas gain energy
and its temperature is increases.
On the other hand, if the gas pushes the piston outside
,so that the gas is expanded , some work is done by the
gas, it losses some of its energy and cool down

Zeroth law of thermodynamics :

Statement: If two systems are in each in thermal equilibrium with a third system ,they are also in
thermal equilibrium with each other.
 Figure shows a schematic representation of
the Zeroth law of thermodynamics.
 The double arrow represents thermal
equilibrium between systems.
 If system A and C are in thermal equilibrium,
and systems A and B are in thermal
equilibrium, then systems B and C must be in
thermal equilibrium.
Then systems A, B and C are at the same
temperature.
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Example : When we use thermometer to measure temperature of object.
when the thermometer and the object are in the equilibrium then the thermometer indicates the
temperature of the object

First law of thermodynamics :

Statement : Energy neither be created nor be destroyed , it can convert one form to another form and
total energy in the Universe remain constant.
 This law gives the mathematical relationship between heat and work.
 Consider a thermodynamic system consist of an ideal gas enclosed in a cylinder with massless,
movable and frictionless piston as shown in figure.
 In this, the gas inside the cylinder is the system and the cylinder along with the piston is its
environment.
 Consider the work done by the system in increasing the volume of the cylinder.
 During expansion , the gas molecule which strike the piston losses their momentum to it and exert
pressure on it. As a result, the piston moves through a finite distance.
 The gas does positive work on the piston.
 When the piston is pushed in so that the volume of the gas decreases, the gas molecules striking it
gain momentum from the piston.
 The gas does a negative work on the piston.

Let A be the cross sectional area of the cylinder (and the piston) and ‘p’ be the constant pressure
exerted by the system on the piston .
Therefore , The total force exerted by the system on the
piston will be
F = pA -------(1)
If the piston moves through an infinitesimal (very small)
distance dx, the work done by this force is,
dW = F. dx
dW = p A.dx
But A dx = dV, the infinitesimal change in the volume of the cylinder.

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Hence, the work done by the system in bringing out this infinitesimal change in the volume is,
dW = p dV -------------(2)
Let Vi be the initial volume of the cylinder and Vf be its volume after some finite change ,
then the total work done in changing the volume of the cylinder is,

W = ∫

W = p ( Vf – Vi ) -----------------(3)
Now we know that the internal energy of a system can be changed either by providing some heat to it
(or, by removing heat from it) or, by doing some work on it.
Equation (3) gives the amount of work done in changing the volume of a system.
When the amount of heat Q is added to the system and the system does not do any work during the
process, its internal energy increases by the amount,
∆U = Q ---------------------(4)
On the other hand, when the system does some work to increase its volume, and no heat is added to it
while expanding, the system loses energy to its surrounding and its internal energy decreases.
This means that when W is positive, ∆U is negative and, vice versa.
Therefore, we can write,
∆U = -W ---------------------------(5)
In practice, the internal energy can change by both the ways.
Therefore, we consider the effect of both together and write the total change in the internal energy as,
∆U = Q - W ---------------------------(6)
This is the mathematical statement of the first law of thermodynamics.
Equation (5) can be written as
Q = ∆U + W ---------------------------(6)
This is the mathematical statement of the first law of thermodynamics.
The quantities W and Q can be positive , negative or zero . Therefore ∆U can be positive , negative or zero

 Figure shows these three cases. Figure (a) shows the case when more heat is added to the system
than the work done by it. The internal energy of the system increases, (∆U > 0)
 Figure (b) shows the case when more work is done by the system than the heat added to it.
In this case, the internal energy of the system decreases, (∆U < 0).
 Figure (c) shows the case when heat added to the system and the work done by it are the same.
The internal energy of the system remains unchanged, (∆U = 0).

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Thermodynamic state variables :
Thermodynamics is not the study of changes in temperature of a system only. As we know when
temperature of a system changes (it gains or releases energy), its other properties can also
change.
Let us understand these properties. We will define the term property of a thermodynamic system
first.
Property of a system or a system variable:
 Any measurable or observable characteristic or property of a system when the system remains in
equilibrium is called a state variable of the system.
 We will use the term variable to describe characteristic of a system.
 For example, pressure, volume, temperature, density and mass of a system are some of the
variables that are used to describe a system.
 These are measurable properties and are called macroscopic variables of a system.

Thermodynamic Equilibrium:
A system is in thermodynamic equilibrium if the following three conditions of equilibrium are satisfied
simultaneously. These are, 1) Mechanical equilibrium, 2) Chemical equilibrium, and 3) Thermal
equilibrium.
1) Mechanical equilibrium:
 A system is said to be in mechanical equilibrium, when there are no unbalanced forces within the
system and between the system and its surrounding.
 The system is also said to be in mechanical equilibrium when the pressure throughout the system
and between the system and its surrounding is the same
2) Chemical equilibrium:
 A system is said to be in chemical equilibrium when its chemical composition is the same
throughout and does not change with time.
 A system is said to be in chemical equilibrium when there are no chemical reactions going on
within the system, or there is no transfer of matter from one part of the system to the other due
to diffusion.
3) Thermal equilibrium:
 A system is said to be in thermal equilibrium , When the temperature of a system is uniform
throughout and does not change with time.

Thermodynamic State Variables and Equation of State :

Every equilibrium state of a thermodynamic system is completely described by macroscopic variables,
called as state variables.
For example, an equilibrium state of a gas is completely described by the values of its pressure p, volume
V, temperature T, and mass m.
 Consider a mixture of gases or vapours as in case of the fuel in an automobile engine.

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 Its state can be described by the state variables but we also need its composition to describe its state.
 A thermodynamic system is not always in equilibrium. Figure
shows such case.
 For example, when an inflated ball is punctured, the air inside
it suddenly expands to the atmosphere.
 This is not an equilibrium state.
 During the rapid expansion, pressure of the air may not be
uniform throughout.
 Similarly, the fuel (a mixture of petrol vapour) in the cylinder of an automobile engine undergoing an
explosive chemical reaction when ignited by a spark is not an equilibrium state.
 This is because its temperature and pressure are not uniform.
 Such system which is not in equilibrium cannot be described in terms of the state variables.
 Eventually, the air in first case, and the fuel in the second case reach a uniform temperature and
pressure and attain thermal and mechanical equilibrium with its surroundings.
 Thus it attains thermodynamic equilibrium.
 In simple words, thermodynamic state variables describe the equilibrium states of a system.
 The various state variables are not always independent.
 They can be mathematically related.

Equation of state :
The mathematical relation between the state variables is called the equation of state.
For example, for an ideal gas, the equation of state is the ideal gas equation,
pV = nRT
Where, p, V and T are the pressure, the volume and the temperature of the gas, n is the number of moles
of the gas and R is the gas constant.
For a fixed amount of the gas, i.e., for given n, there are only two independent variables.
It could be p and V, or p and T, or V and T.

p - V diagram :
The graphical representation of equation of state of a system (of a gas) is called the p - V diagram, or the
p - V curve (the pressure – volume curve), or the indicator diagram of the system.
Figure shows a typical p-V diagram for an ideal gas at some constant temperature .
Isotherm : The pressure-volume curve for a constant temperature is called an isotherm.
Real gases may have more complicated equations of state and
therefore, a complicated p-V diagram.
The equation of state of a system (usually a gas confined to a
cylinder with a movable, frictionless and massless piston) and
its p - V diagram are very useful in studying its behavior.

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Some systems and their behavior using p - V diagrams :
Let Vi be the initial volume of the cylinder and Vf be its volume after some finite change ,then the total
work done in changing the volume of the cylinder is,

W = ∫

W = p ( Vf – Vi ) -----------------(1)
The integral in this equation can be evaluated if we know the relation between the pressure p and the
volume V, or the path between the limits of integration.
Equation. (1) can be represented graphically.
A gas confined to a cylinder with a movable, frictionless, and massless piston can be,
1) expanded with varying pressure (Figure a), or
2) it can be compressed with varying pressure Fig. 4 (b), or
3) it can expand at constant pressure Fig. (c).
Area under curve in the p-V diagram, is the graphical representation of the value of the integral in Eq. (1).
Since this integral represents the work done in changing the volume of the gas, the area under the p-V
curve also represents the work done in this process.

Thermodynamic Process:
A process in which the initial state of a system changes to its final state is called as Thermodynamic
process.
During such process, there may be a transfer of heat into the system from its environment, (positive
heat),
Example : when water boils, heat is transferred to water.
 Heat may be released from the system to its environment (negative heat).
 Similarly, some work can be done by the system (positive work), or some work can be done on the
system (negative work).

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 When the piston in a cylinder is pushed in, some work is done on the system. We know that these
changes should occur infinitesimally slowly so that the system is always in thermodynamic
equilibrium. Such processes in which changes in the state variables of a system occur infinitesimally
slowly are called quasi static systems.
 When a thermodynamic system changes from its initial state to its final state, it passes through a
series of intermediate states.
 This series of intermediate states when plotted on a p - V diagram is called a path.
 The p - V curve or the p - V diagram, shown in above Fig. a, fig b and fig c is such a path.
 It tells us the way a system has gone through a change.

Work Done During a Thermodynamic Process:

1. Consider Fig. (a) which describes different ways in
which we can change the state of a system.
2. The system is initially at state A on the p-V diagram.
Let A( Vi, Pi ) be the initial state and B( Vf,Pf ) be the
final state of system..
3. When the system changes itself from A to B along the
path 1, both its pressure and volume change.
The pressure decreases while the volume increases.
4. The work done by the system is positive (because the volume increases).
It is given by the area under the curve 1 as shown in
the Fig. (b).
5. Second way to change the state from A to state B is path 2
as shown in Fig. (c).
6. In this case, the volume increases to Vf from the point A up
to the point C at the constant pressure Pi .
The pressure then decrease to Pf as shown. The volume
remains constant during this change. The system is now in
the state
7. The work done in this process is represented by the
shaded area under the curve 2 as in Fig. (c).
8. Third way to change the state from A to state B is path 3 as
shown in Fig. (d).
9. In this case, the pressure decreases from Pi to Pf but the
volume remains the same.
Next, the volume changes to Vf at constant pressure Pf .
10. The work done in this process is represented by the
shaded area under the curve 3 as in Fig. (d).
11. We conclude that the work done by a system depends
not only on the initial and the final states, but also on
the intermediate states, i.e. on the paths along which
the change takes place.

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Heat Added During a Thermodynamic Process:

1. Thermodynamic state of a system can be changed
by adding heat also.
2. Consider a thermodynamic system consisting of an
ideal gas confined to a cylinder with a movable,
frictionless, and massless piston.
3. Suppose we want to change the initial volume Vi of
the gas to the final volume Vf at a constant
temperature.
4. There are two different ways in which this change
in volume can be made. Figure (a) shows the first
method.
5. In this case, the gas is heated slowly, in a controlled manner so that it expands at a constant
temperature.
6. It reaches the final volume Vf isothermally.
7. The system absorbs a finite amount of heat during this process.
8. In the second case, shown in Fig. (b) gas cylinder is now surrounded by an insulating material and
it is divided into two compartments by a thin, breakable partition.
9. The compartment X has a volume Vi and the compartment Y has a volume V' i
so that Vi +V'i = Vf .
10. The compartment X of the cylinder is filled with the same amount of gas at the same temperature
as that in the first case shown in the Fig. (a).
11. The compartment Y is empty, it
contains no gas particles or any
other form of matter.
12. The initial state of the system is the
same in both cases.
13. The partition is now suddenly
broken.
14. This causes a sudden, uncontrolled
expansion of the volume of the gas.
15. The gas occupies the volume that
was empty before the partition is
broken.
16. There is no exchange of heat between the gas and its environment because the cylinder is now
surrounded by an insulating material.
17. The final volume of the system after the partition is broken is Vf .
18. In this case, the gas has not done any work during its expansion because it has not pushed any
piston or any other surface for its expansion.
Such expansion is called free expansion.
Example of free expansion is abrupt puncturing of an inflated balloon or a tyre.
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19. It is experimentally observed that when an ideal gas undergoes a free expansion, there is no
change of temperature.
20. Therefore, the final state of the gas in this case also, is the same as the first case.
21. The intermediate states or the paths during the change of state in the first and the second case
are different. But the initial and the final states are the same in both cases.
22. Figures (a) and (b) represent two different ways of taking a system from the initial state to the
final state.
23. This means we have two different paths connecting the same initial and the final states of a
system.
24. In case of the method shown in Fig. 4.13 (a) there is an exchange of heat. In case of the method
shown in Fig. (b), there is no exchange of heat and also, the system does not do any work at all
because there is no displacement of any piston or any other surface.
25. To conclude, heat transferred to a system also depends on the path.

Classification of Thermodynamic Processes:

1. A process by which two or more of these variables can be changed is called a thermodynamic
process or a thermodynamic change.
2. Thermodynamic state can be described by its pressure p, volume V, and temperature T.
3. These are the state variables of a system.
4. As we have discussed earlier, there can be a number of different ways to change these
parameters, that is, there are different thermodynamic processes.
5. But in practice, for the sake of measurement, any one of the state variables is held constant and
other two are varied.
6. This leads us to a very useful way of classifying thermodynamic processes.

Reversible and Irreversible Processes:

1. Reversible Processes :
A process is a change that can be retraced in reverse (opposite) direction is called as Reversible
Process.
 The path of a reversible thermodynamic process is the same in the forward and the reverse
direction.
 That means the initial sates of the system can be
restored.
 Fig (a) shows path of reversible thermodynamic process.
 e.g. melting of ice, freezing of water, boiling of water,
condensation of steam can be reversed.
 This path shows a reversible expansion of a gas followed
by its reversible compression.
 Such changes are very slow and there is no loss of any energy in the process and the system is
back to its initial state after it is taken along the reverse path.
 Reversible processes are ideal processes.
 A real thermodynamic process will always encounter some loss due to friction or some other
dissipative forces.
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2. Irreversible Processes:
A process is a change that cannot be retraced in reverse (opposite) direction is called as Irreversible
Process.
 The path of a irreversible thermodynamic process is
not same in the forward and the reverse direction.
That means the initial sates of the system cannot be
restored.
 e.g Puncturing an inflated balloon or a tyre, rubbing
our palms together, burning a candle.
 Fig (b) shows the path of irreversible thermodynamic process.
 There is a permanent loss of energy from the system due to friction or other dissipative forces in
an irreversible processes.
 The change of state depends on the path taken to change the state during an irreversible process.
 An irreversible process shows a hysteresis.

Cause of Irreversibility:
There are two main reasons of the irreversibility of a thermodynamic process
1. Many processes such as a free expansion or an explosive chemical reaction take the system to
non-equilibrium states.
2. Most processes involve friction, viscosity or some other dissipative forces.

Assumptions for discussion of thermodynamic processes:

We will be discussing various types of thermodynamic systems in the following sections
There are some assumptions for discussing various types of thermodynamic processes.
i) Majority of the thermodynamic processes we will be discussing in the following sections
are reversible. That is, they are quasistatic in nature.
ii) They are extremely slow and the system undergoes infinitesimal change at every stage
except the adiabatic processes. The system is, therefore, in thermodynamic equilibrium
during all the change.
iii) The ‘system’ involved in all the processes is an ideal gas enclosed in a cylinder having a
movable, frictionless, and massless piston.
iv) Depending on the requirements of the process, the walls of the cylinder can be good
thermal conductors (for an isothermal process) or can be thermally insulating (for an
adiabatic process).
v) The ideal gas equation is applicable to the system.

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1. Isothermal process:
A process in which change in pressure and volume takes place at a constant temperature is called an
isothermal process.
 For such a system ∆T = 0.
 Isothermal process is a constant temperature process.
 This is possible when a system is in good thermal contact
with its environment, and the transfer of heat from, or to
the system, is extremely slow so that thermal equilibrium
is maintained throughout the change.
e.g. melting of ice, which takes place at constant
temperature, is an isothermal process.
For an isothermal process,
1. Equation of state : PV = constant
2. ∆T = 0 constant temperature process
3. ∆U = 0 no change in internal energy
4. Q = W energy exchange is used to do work
5. W = P ∆V
6. An isothermal change is very slow change.

Thermodynamics of Isothermal Process:

The temperature of a system remains constant in an isothermal change and Boyle’s law can be applied to
study these changes.
Therefore, the equation of state for an isothermal change is given by,
PV = constant ------------- (1)
If pi , Vi and Pf , Vf are the variables of a system in its initial and the final states respectively, then for an
isothermal change,
Pi Vi = P f Vf = constant.
Consider the isothermal expansion of an ideal gas.
During this process , small work is done and it is given by

W = ∫

W = ∫ ---------------------------(2)

We know, for an ideal gas , PV = nRT

W = ∫

W = nRT ∫

W = nRT [log V ]

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W = nRT [log Vf- log Vi ]

W = nRT log ( ) ---------------------(3)

For an ideal gas, its internal energy depends on its

temperature.
Therefore, during an isothermal process, the internal
energy of an ideal gas remains constant (∆U = 0) because
its temperature is constant (∆T = 0).When First law of
thermodynamics applied to an isothermal process, then it
can be written as
Q = W

Q = nRT log ( ) ---------------------(4)

Thus, the heat transferred to the gas is completely converted into the work done, i.e., for expansion of
the gas. when the gas absorbs heat, it does positive work and its volume expands.
When the gas is compressed, it releases heat and it does negative work.
Following figure shows P-V diagram of an isothermal process .
Any change of phase occurs at a constant temperature, and therefore, it is called as an isothermal
process.

2. Isobaric process:
A process which takes place at a constant pressure is called an isobaric process.
 For an isobaric process, none of the quantities
∆U, Q and W is zero.
 It is a constant pressure process.
 Boiling water at constant pressure, normally at
atmospheric pressure, is an isobaric process.
 Figure shows the p-V diagram of an isobaric process.
It is called as an isobar.

Thermodynamics of Isobaric process:

The pressure of a system remains constant in this process i.e. ∆ p = 0.
Consider an ideal gas undergoing volume expansion at constant pressure.
If Vi and Ti are its volume and temperature in the initial state of a system and Vf and Tf are its final
volume and temperature respectively, the work done in the expansion is given by
W = p dV
W = p ( Vf – Vi)
W = nR ( Tf – Ti) -------------------(1)
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The change in internal energy of a system is given by
∆U = n Cv ∆T
∆U = n Cv (Tf – Ti) ---------------------------(2)
According to first law of thermodynamics
Q = ∆U + W -----------------------(3)
From equation (1) , (2) and (3), we get,
Q = n Cv (Tf – Ti) + nR ( Tf – Ti)
Q = ( n Cv + nR ) (Tf – Ti)
Q = n ( Cv + R ) (Tf – Ti)
But Cv + R = Cp
Q = n Cp (Tf – Ti) ---------------------(4)
From equation (4) , we can say that temperature of system changes in an isobaric process. Therefore
its internal energy also increases. The heat exchange is partly used for increasing temperature and
partly to do some work.

3. Isochoric process:
A process which takes place at a constant volume is called an isochoric process.
 It is a constant volume process.
 A system does no work on its environment during an isochoric change.
 Figure shows the p-V diagram of an isochoric process.
 For an isochoric process, ∆V =0,
Therefore the first law of thermodynamics is ,
∆U = Q.
This means that for an isochoric change, all the energy
added in the form of heat remains in the system itself and
causes an increase in its internal energy.
e.g. Heating a gas in a constant volume container or
diffusion of a gas in a closed chamber

Thermodynamics of Isochoric process:

For an isochoric process, , ∆V =0.
The system does not do any work and all the energy supplied to the system is converted into its
internal energy.
The first law of thermodynamics for isochoric process is
Q = ∆U -------- --- (1)
The change in internal energy is given by
∆U = n Cv ∆T -----------------(2)
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The work done is given by
W = p∆V = 0 ----------------(3) (because ∆V = 0).
The heat exchanged is given by the first law of thermodynamics,
Q = ∆U + W
= ∆U + 0
Q = ∆U
Q = n Cv ∆T ------------ (4)

5. Adiabatic process:
A process in which there is no transfer of heat from or to the system is called as Adiabatic Process .
 For an adiabatic change, Q = 0.
 Heat transfer to or from the system is prevented by either
perfectly insulating the system from its environment, or by
carrying out the change rapidly so that there is no time for
any exchange of heat.
 Figure shows the p-V diagram of an adiabatic process.
 e.g. Puncturing an inflated balloon or a tyre are some
familiar examples of adiabatic changes.

For an adiabatic change,

∆U = -W ------------ (1)
When a system expands adiabatically, W is positive (work is done by the system) and ∆U is
negative, the internal energy of the system decreases.
When a system is compressed adiabatically, W is negative (work is done on the system), and ∆U is
positive. the internal energy of the system increases.

Thermodynamics of Adiabatic process:

For an adiabatic process ,

pVγ = constant = C ------------------ (1)

where, γ is the ratio of the specific heat at constant pressure to the specific heat at constant volume, i.e.,

γ=

γ is also called adiabatic ratio.

For moderate temperature changes, the value of γ is for monoatomic gases,

for diatomic gases and for polyatomic gases.

When a system undergoes an adiabatic change, its temperature and internal energy both change.
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 More Sir’s Physics Notes
The change in internal energy is,
∆U = Cv (∆T) ------------- (2)
The work done is

Equation (5) implies that when work is done by the gas, i.e., when the gas expands, W > 0, and Ti > Tf .
This mean that the gas will cool down.
Similarly, if the work is done on the gas, i.e., if the gas is compressed W < 0, and Ti < Tf This means that
the gas will warm up.

6. Cyclic Process:
A thermodynamic process that returns a system to its initial state is calleda cyclic process.
In this process, the initial and the final state is the same.
Figure shows the p-V diagram of a cyclic process.
For a cyclic process,
the total change in the internal energy of a system is zero.
i.e. ∆U = 0.
According to the first law of thermodynamics, , for a cyclic
process,
Q = W ------- (1)

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 More Sir’s Physics Notes
7. Free Expansion:
These expansions are adiabatic expansions and there is no exchange of heat between a system and its
environment.
Also, there is no work done on the system or by the system.
Q = W = 0 -----------------------(1)
According to the first law of thermodynamics,
Q = ∆U + W ------------------(2)
From equation (1) and (2) , we get
∆U = 0
e.g , when a balloon is ruptured suddenly, or a tyre is suddenly punctured, the air inside rushes out
rapidly but there is no displacement of a piston or any other surface.
 Free expansion is different than other thermodynamic processes
 It is an uncontrolled change.
 It is an instantaneous change and the system is not in thermodynamic equilibrium.
 A free expansion cannot be plotted on a p-V diagram.
 Only its initial and the final state can be plotted.

Heat Engines:
 A machines that converts heat partly into work or mechanical energy is called as Heat engines.
 It works by using cyclic processes and involve thermodynamic changes.
e.g Automobile engines
 A heat engine receives heat from a source called reservoir and converts some of it into work ,
Some heat is lost in the form of exhaust.
A typical heat engine has the following elements:
(1) A working substance:
 It is called the system. It can be an ideal gas for an ideal heat engine .
 The working substance can be a mixture of fuel vapour and air in a gasoline (petrol) or
diesel engine, or steam in a steam engine.
 It is the working substance that absorbs heat and does work.
(2) Hot and cold reservoir:
 The working substance interacts with the reservoirs.
 The hot reservoir is the source of heat.
 It is at a relatively high temperature and is capable of providing large amount of heat at
constant higher temperature, TH.
 It is also called as the source.
 The cold reservoir absorbs large amount of heat from the working substance at constant
lower temperature, TC. It is also called as the sink.
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 More Sir’s Physics Notes
(3) Cylinder:
 Generally, the working substance is enclosed in a cylinder with a moving, frictionless, and
massless piston.
 The working substance does some work by displacing the piston in the cylinder.
 This displacement is transferred to the environment using some arrangement such as a
crank shaft which transfers mechanical energy to the wheels of a vehicle.
Heat engines are of two basic types. They differ in the way the working substance absorbs heat.
I. External combustion engine: In this engine, the working substance is heated externally as in case
of a steam engine.
II. Internal combustion engine: In this engine , the working substance is heated internally similar to
an automobile engine using gasoline or diesel.
Any heat engine works in following three basic .
1. The working substance absorbs heat from a hot reservoir at higher temperature.
2. Part of the heat absorbed by the working substance is converted into work.
3. The remaining heat is transferred to a cold reservoir at lower temperature.
Heat engines are classified according to the working substance used and the way these steps are actually
implemented during its operation.
Heat engines are diagrammatically represented by an energy flow diagram schematically shown in
Figure..
Energy exchange takes place during various stages of working of a heat engine.
Let QH be the heat absorbed by the working
substance at the source, and
QC be the heat rejected by it at the sink. In a heat
engine, QH is positive and QC is negative.
Also, let W be the work done by the working
substance.
 In the Figure, the circle represents the
engine.
 The ‘heat pipelines’ shown in the diagram
represent the heat absorbed, rejected,
and converted into work.
 The width of the heat ‘pipeline’ indicated
by QH, is proportional to the amount of
heat absorbed at the source.
 Width of the branch indicated by QC is proportional to the magnitude | QC | of the amount of heat
rejected at the sink.
 Width of the branch of the pipeline indicated by W is proportional to the part of the heat
converted into mechanical work.
 One single execution of the steps mentioned above is one operating ‘cycle’ of the engine.
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 More Sir’s Physics Notes
 Several such cycles are repeated when a heat engine operates.
 The quantities QH and QC represent the amount of heat absorbed (positive) and rejected
(negative) respectivety during one cycle of operation
The net heat Q absorbed per operating cycle is,
Q = QH + Qc = | |-| | --- (1)
According to first law of thermodynamics, the net work done in one operating cycle, by the working
substance, is given by
W = Q = | |-| | ------ - --- (2)
The thermal efficiency η of the heat engine is defined as,

η = ------ - --- (3)

from equation (1) , (2) and (3) we get

η = = 1+
| |
η = 1 - | |
------------------------(4)

Equation (4) gives the thermal efficiency of a heat engine.

The Heat Engine Cycle and the p-V Diagram:

We know, the working of a heat engine is a well defined sequence of operations.
It is a cyclic thermodynamic process.
We will now discuss the p-V diagram of a heat engine.
Heat is absorbed in one part of the cycle, work is done
in another part, and the unused heat is rejected in yet
other part of the cycle.
The p-V diagram of a typical heat engine is shown in
the following Figure.
 The operating cycle begins at the point A in the
cycle.
 The working substance, the gas in this case,
absorbs heat at constant volume and no work is
done by the gas or on the gas.
 The pressure is increased till the point B is reached.
 The temperature of the gas also increases and its internal energy increases.
 The gas starts expanding by pushing the piston away and its volume changes from the point B to the
point C.

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 More Sir’s Physics Notes
 Because the gas expands, its pressure is reduced. The gas does work in this part of the cycle.
 When the point C is reached, the excess heat, the heat that is not utilized in doing work by the gas,
is rejected. The gas cools down and its internal energy decreases.
 This process is again at constant volume.
 The pressure of the gas is reduced and point D on the p-V diagram is reached.
 The gas is now compressed. Its volume decreases and its pressure increases.
 The change continues till the point A is reached.
 The cycle is complete and the system is ready for the next cycle.
 Thus, the p-V diagram is a visual tool for the study of heat engines.
 The operation of a heat engine is a cyclic process therefore, its p-V diagram is a closed loop.
 The area of the loop represents the work done during one complete cycle.

 Since work is done by the gas, or on the gas, only when its volume changes, the p-V diagram
provides a visual interpretation of the work done during one complete cycle. Similarly, the internal
energy of the gas depends upon its temperature.
Hence, the p-V diagram along with the temperatures calculated from the ideal gas law determines
the changes in the internal energy of the gas.
We can calculate the amount of heat added or rejected from the first law of thermodynamics.
Thus, a p-V diagram helps us analyze the performance of any heat engine which uses a gas as its
working substance.

Refrigerators and Heat Pumps:

 Refrigerators and heat pumps are heat engines that work in backward direction.
 They convert mechanical work into heat.

Heat Flow from a Colder Region to a Hotter Region:

1. According to the second law of thermodynamics , heat cannot flow from a region of lower
temperature to a region of higher temperature on its own.
2. We can force heat to flow from a region of lower temperature to a region of higher temperature
by doing work on the system (or, on the working substance of a heat engine).
3. Refrigerators or air-conditioners and heat pumps are examples of heat engines which cause heat
to be transferred from a cold region to a hot region.
4. Usually, this is achieved with the aid of phase change of a fluid, called the refrigerant.
5. The refrigerant is forced to evaporate and then condense by successively decreasing and
increasing its pressure.
6. It can, therefore, ‘pump’ energy from a region at lower temperature to a region of higher
temperature.
7. It extracts the heat of vaporization of the refrigerant from the cold region and rejects it to the
hotter region outside the refrigerator.

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 More Sir’s Physics Notes
8. This results in cooling down the cold region further.
9. Figure shows the concept of transferring heat from a cold region to a hot region in a schematic
way.
10. Heat from the cold region is carried to the hot region by the refrigerant.
11. It extracts heat from a cold region due to forced evaporation.
12. The heat of evaporation of the refrigerant thus absorbed is rejected by compressing and
condensing it into liquid at a higher temperature.
13. All this process is carried out in a mechanism involving a compressor and closed tubing such as
seen at the back of a house hold refrigerator.

Refrigerator:
 Refrigeration is a process of cooling a space or substance of a system and/or to maintain its
temperature below its ambient temperature.
 In simple words, refrigeration is artificial cooling.
 A refrigerator extracts heat from a cold region (inside the chamber, or the compartments) and
delivers it to the surrounding (the atmosphere) thus, further cooling the cold region.
 Figure (a) shows the schematics of the
mechanism used in a typical refrigerator.
 It consists of a compressor, an expansion valve,
and a closed tube which carries the refrigerant.
 Part of the tube, called the cooling coil, is in the
region which is to be cooed at lower
temperature and lower pressure.
 The other part which is exposed to the
surrounding (generally, the atmosphere) is at a
higher temperature and higher pressure.
 A fluid such as (fluorinated hydrocarbons) is
used as refrigerant. Normally, the cold and the hot part of the coil contain the refrigerant as a
mixture of liquid and vapour phase in equilibrium
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 More Sir’s Physics Notes
 Figure (b) shows the energy flow diagram of a refrigerator.
 The heat extracted from a cold reservoir is
supplemented by the mechanical work done (on the
refrigerant) by the compressor and the total energy is
rejected at the hot reservoir.
 The refrigerant goes through the following steps in one
complete cycle of refrigeration.
Step 1: The fluid passes through a nozzle and expands into a
low-pressure area. Similar to the way carbon dioxide comes
out of a fire extinguisher and cools down, the fluid turns into
a gas and cools down. This is essentially an adiabatic
expansion.

Step 2: The cool gas is in thermal contact with the inner

compartment of the fridge. It heats up as heat is transferred to it from the contents of the fridge. This
takes place at constant pressure, so it's an isobaric expansion.

Step 3: The gas is transferred to a compressor, which does most of the work in this process. The gas is
compressed adiabatically, heating it and turning it back to a liquid.

Step 4: The hot liquid passes through coils on the outside of the fridge, and heat is transferred to the
atmosphere. This is an isobaric compression process. The compressor is driven by an external energy
source and it does the work |W| on the working substance during each cycle.

Performance of a Refrigerator:
Consider the energy flow diagram of a refrigerator Fig. (b).
It shows the relation between the work and heat involved in transferring heat from a low temperature
region to a high temperature region.
This is a cyclic process in which the working substance, the refrigerant is taken back to the initial state.
For a refrigerator, the heat absorbed by the working substance is QC and the heat rejected by it is QH.
A refrigerator absorbs heat at lower temperature and rejects it at higher temperature, therefore, we
have, QC > 0, QH < 0, and W < 0.
Hence, we write, |W| and |QH| = - QH.
In this case, we apply the first law of thermodynamics to the cyclic process.
For a cyclic process, the internal energy of the system in the initial state and the final state is the same,
therefore, QH + QC = W , or QH + QC -W = 0
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 More Sir’s Physics Notes
-QH = QC - W
For a refrigerator, QH < 0, and W < 0,
therefore, |QH| = |Qc| + |W| ------------------------(1)
From the Fig. (b), we realize that the heat |QH rejected by the working substance at the hot reservoir is
always greater than the heat QC received by it at the cold reservoir.
| |
The ratio | |
indicates the performance of a refrigerator and is called the coefficient of performance
(CoP), K, or quality factor, or Q-value of a refrigerator.
Larger is the ratio, better is the refrigerator.
That means a refrigerator has the best performance when the heat extracted by the refrigerant at the
cold reservoir is maximum by doing minimum work in one operating cycle.
From Eq. (1), |W| = |Qc| - |QH|
| | | |
K= | |
= ---------- (2)
| | | |

All the quantities on the right side of Eq. (2) represent energy and are measured in the same energy units.
The coefficient of performance, K of a refrigerator is, therefore, a dimensionless number. For a typical
household refrigerator, K ≈ 5.

Air conditioner:
1. Working of an air conditioner and a refrigerator is exactly similar.
2. It differs from a refrigerator only in the volume of the chamber/ room it cools down.
3. For an air conditioner, the evaporator coils are inside the room that is to be cooled and the
condenser is outside the room.
4. The air cooled by the evaporator coils inside the room is circulated by a fan placed inside the air
conditioning unit.
| |
5. The performance of an air conditioner is defined by K = | |
.
6. It is important to consider the rate of heat removed H and the power P required for removing the
heat.
| |
7. We define the rate of heat removed as the heat current H = , where, t is the time in which
heat Qc is removed.
| |
8. Therefore, the coefficient of performance of an air conditioner can be calculated as, K = | |
=
=

Typical values of K are 2.5 to 3.0 for room air conditioners.

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 More Sir’s Physics Notes
Heat Pump:
 Heat pump is a device which works similar to a refrigerator.
 It is used to heat a building or a similar larger structure by cooling the air outside it.
 A heat pump works like a refrigerator operating inside out.
 In this case, the evaporator coils are outside and absorb heat from the cold air from outside.
 The condenser coils are inside the building.
 They release the absorbed heat to the air inside the thus, warming the building.

Limitations of the First Law of Thermodynamics:

1. The First law of thermodynamics tells us that heat can be converted into work and work can also
be converted into heat.
2. It has the following limitations.
(a) It does not tell us whether any particular process can actually occur. According to the first law
of thermodynamics, heat may, on its own, flow from an object at higher temperature to one at
lower temperature and it can also, on its own, flow from an object at lower temperature to one
at higher temperature.
We know that practically, heat cannot flow from an object at lower temperature to another at
higher temperature. The First law of thermodynamics does not predict this practical
observation.
(b) According to the First law, we could convert all (100%) of the heat available to us into work.
Similarly, all the work could be converted into heat. Again, we know that practically this is not
possible.
Thus, the First law of thermodynamics does not prevent us from converting heat entirely into
work or work entirely into heat.
These limitations lead to the formulation of another law of thermodynamics called the Second law
of thermodynamics.

Second law of thermodynamics :

Kelvin Planck statement :
“It is impossible to extract an amount of heat QH from a hot
reservoir and use it all to do work W. Some amount of heat QC must
be exhausted to a cold reservoir”.
It is also called as the ‘Engine Law’ or the ‘Engine Statement’ of the
Second law of thermodynamics.
Figure is a diagrammatic representation of the application of the
Second law of thermodynamics to a heat engine.
From Figure (a), all heat engines lose some heat to the environment
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 More Sir’s Physics Notes
of a perfect heat engine. All the heat QH, extracted can not be used to do work.
Figure (b) shows the energy flow diagram for such a situation.

Clausius’s Statement :

“It is not possible for heat to flow from a colder body to a

warmer body without any work having been done to
accomplish this flow”.

It is also called as the ‘Refrigerator Law’ or the ‘Refrigerator

Statement’ of the Second law of thermodynamics.

This means that energy will not flow spontaneously from an

object at low temperature to an object at a higher
temperature. This rules out the possibility of a perfect
refrigerator.

The statements about refrigerators are also applicable to

air conditioners and heat pumps, which work on the same
principles.

Figure (a) and (b) is a diagrammatic representation of the

application of the Second law of thermodynamics to a refrigerator.

Fig. (a), a practical refrigerator requires work W to be done to extract heat QH from a cold reservoir and
reject it to a hot reservoir.

The statement means that spontaneous flow of heat from an object at cold temperature is not possible
Fig. (b).

Carnot Cycle and Carnot Engine:

1. Significance of Reversibility in Thermodynamics:
I. A reversible process is a ‘bidirectional’ process, i.e., it follows exactly the same steps in either
direction.
II. This requires the process to take place in infinitesimally small steps.
III. Also, the difference between the state variables in the two infinitesimally close states should
be very small.
IV. This would be possible if the system is in thermodynamic equilibrium with its environment
throughout the change.
V. An irreversible process, on the contrary, is a unidirectional process.
VI. It can take place in only in one direction.
VII. Any irreversible process is not in thermal equilibrium with its environment

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 More Sir’s Physics Notes
Maximum Efficiency of a Heat Engine and Carnot’s Cycle:
We know that conversion of work to heat is an irreversible process.
A heat engine would convert maximum heat into work if all irreversible processes could be avoided.
In that case, the efficiency of the heat engine can be maximum.
Carnot, French engineer and scientist, proposed a hypothetical ideal engine in 1824 which has the
maximum efficiency.
In a carnot engine, there are basically two processes:
(i) Exchange of heat (steps A to B and C to D in the Fig. ):
For this to be reversible, the heat exchange
must be isothermal.
This is possible if the working substance is at
the temperature TH of the source while
absorbing heat.
The working substance should be at the
temperature of the cold reservoir TC, while
rejecting the heat.
(ii) Work done (steps B to C and D to A).:
For work done to be reversible, the process
should be adiabatic.
Thus, the cycle includes two isothermal and
two adiabatic processes for maximum
efficiency.
The corresponding p-V diagram will then be
as shown in the Fig..
By using the expression for work done during an adiabatic and an isothermal process E, we can
derive an expression for the efficiency of a Carnot cycle/engine as,

η = ------ - --- (1)

η = = 1+
| |
η = 1 - | |
------------------------(2)

η = 1 -

Thus, while designing a heat engine for maximum efficiency, the source temperature T H should be as high
as possible and the sink temperature TC should be as low as possible.

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Carnot Refrigerator:
We know that a refrigerator is nothing but a heat engine operated in the reverse direction.
Because each step in the Carnot cycle is reversible, the entire Carnot cycle is reversible.
If we operate the Carnot engine in the reverse direction, we get the Carnot refrigerator.
The coefficient of performance of a Carnot refrigerator as,

Equation (2) gives the coefficient of performance of an ideal refrigerator or, the Carnot refrigerator.
It says that the coefficient of performance of a Carnot refrigerator also depends on only the temperature
difference of the hot and the cold reservoir.
When the temperature difference is very small, the coefficient is very large.
In this case, a large quantity of heat can be removed from the lower temperature to the higher
temperature by doing very small amount of work.
The coefficient of performance is very small when the temperature difference is large.
That means a small quantity of heat will be removed even when a large amount of work is done

The Second Law of Thermodynamics and the Carnot Cycle:

"The Carnot engine is the most efficient heat engine.
Also, all Carnot engines operating between the same two temperatures have the same efficiency,
irrespective of the nature of the working substance".
We have made two very important statements here.
1. Carnot engine is the most efficient heat engine, and
2. Efficiency of a Carnot engine is independent of its working substance.
We can also show that “A Carnot refrigerator has a greater coefficient of performance among all the
refrigerators working between the same two temperatures.”

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Sterling Cycle:
 This is a closed thermodynamic cycle.
 The Sterling engine is based on this cycle
shown in Figure.
 The working substance used in a Sterling
engine is air, helium, hydrogen, nitrogen etc.
 All the processes in the Sterling cycle are
reversible processes.
 When the gas is heated, the Sterling engine
produces useful work.
 When work is done on the gas, it works as a
refrigerator.
 This is reverse working of a Sterling cycle.
 The reversed Sterling cycle is extensively used
in the field of cryogenics to produce
extremely low temperatures or to liquefy air
or gases mentioned above.
 The ideal Sterling cycle has two isothermal processes AB and CD.
 Two isobaric processes BC and DA connect the two isothermal processes.
 Heat is absorbed at constant temperature TH and rejected at constant temperature TC.
 The four processes in a Sterling cycle are described briefly in the following.
I. Isothermal expansion (AB):
The gas is heated by supplying heat QH at constant temperature TH.
Useful work is done by the gas in this part of the cycle.
II. Isochoric process (BC):
Part of the heat absorbed (QH) by the gas in the previous part of the cycle is released by the gas
to the refrigerator.
This heat (Q) is used in the next part of the cycle.
The gas cools down to temperature TC.

III. Isothermal compression (CD):

The heat generated in this part of the cycle (QC) is rejected to the coolant (sink).
The temperature of the gas is maintained at TC during this process.
IV. Isobaric heat absorption (DA):
The compressed gas absorbs heat (Q) during this process.
Its temperature is increased to TH.
The cycle repeats when the process reaches the point A.

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