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Chapter 12 - Thermodynamics
PHYSICS DERIVATIONS
1. FIRST LAW OF THERMODYNAMICS:-

Let Heat supplied to the system by the surroundings

Work done by the system on the surroundings

Change in internal energy of the system

Then according to the first law of thermodynamics,

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As shown in the figure above, suppose the system is a gas contained in a
cylinder provided with a movable piston.

Then the gas does work in moving the piston. The work done by the system
against a constant pressure is

Force Distance Pressure area Distance

Or

Where the change in the volume of the gas.

So the first law of thermodynamics takes the form,

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2. RELATION BETWEEN AND :-

Consider one mole of an ideal gas. Heat the gas to raise its temperature by .
According to the first law of thermodynamics, the heat supplied is used
partly to increase the internal energy and partly in doing the work of
expansion. That is,

If the heat is absorbed at constant volume, then and we have

( ) ( ) ( )

We have dropped the subscript because the internal energy of an ideal

gas depends only on its temperature .

If now the heat is absorbed at constant pressure, then

( ) ( ) ( )

( ) ( )

Again, we have dropped the subscript from the first term because of an
ideal gas depends only on .

Clearly

( )

But for one mole of an ideal gas,

Differentiating both sides w.r.t. for constant pressure ,

( ) ( )

Or

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 ( )

Hence

3. WORK DONE IN AN ISOTHERMAL PROCESS:-

Consider moles of an ideal gas contained in a cylinder having conducting

walls and provided with frictionless and movable piston, as shown in the
figure above. Let be the pressure of the gas.

Work done by the gas when the piston moves up through a small distance
is given by

Where is the cross-sectional area of the piston and , is the small

increase in the volume of the gas. Suppose the gas expands isothermally from
initial state ( ) to the final state ( ). The total amount of work done
will be

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 ∫

For moles of a gas,

Or

∫ ∫

Or

4. ADIABATIC RELATIONS BETWEEN AND :-

(1) ADIABATIC RELATION BETWEEN AND :

According to the first law of thermodynamics,

For one mole of a gas,

And

Also, for an adiabatic process,

According to the ideal gas equation,

Differentiating both sides, we get

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Or

Or

Or
( )
Or

Dividing both sides by , we get

Or

Integrating both sides, we get

∫ ∫

Where is constant of integration

Or

Or

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Or

Where is another constant.

(2) ADIABATIC RELATION BETWEEN AND :

For one mole of a gas , therefore

Putting , we get

( )

Or

i.e.,

(3) ADIABATIC RELATION BETWEEN AND :

Again, for one mole of a gas , therefore

Putting in , we get

Or

i.e.,
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5. WORK DONE IN AN ADIABATIC PROCESS:-

Consider moles of an ideal gas contained in a cylinder having insulating walls

and provided with frictionless and insulating piston. Let be the pressure of
the gas. When the piston moves up through a small distance the work
done by the gas will be

Where is the cross-sectional area of the piston and is the

increase in the volume of the gas.

Suppose the gas expands adiabatically and changes from the initial state
( ) to the final state ( ) The total work done by the gas will
be

For an adiabatic change

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Or

∫ [ ]

[ ] [ ]

But

[ ]

Or

Also,

And

Or

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6. FIRST LAW OF THERMODYNAMIC APPLIED TO ISOBARIC PROCESS:-

FIRST LAW OF THERMODYNAMICS APPLIED TO AN ISOBARIC PROCESS:

A Thermodynamic process which occurs at a constant pressure is called an
isobaric process.
Suppose the pressure of a gas remains constant and its volume changes
from to , then the work done by the gas is

∫ ∫ ( )

( )
BOILING PROCESS:

Suppose mass of a liquid is heated at the temperature of its boiling point so

that it changes into vapour at a pressure . Let be the volume of the liquid
and that of vapour. The work done by the liquid during its expansion at
temperature is given by
( )
Let be the heat of vaporisation of the liquid. T represents the heat needed
per unit mass to change from liquid to vapour phase at constant temperature
and pressure. Then the amount of heat required for vaporisation of mass of
liquid will be

Let and be the initial and final values of internal energy. According to
the first law of thermodynamics,

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Or
( )
Or
( )

MELTING PROCESS:

Suppose mass of a solid is heated at its melting point. When the solid melts,
the change in its volume is negligibly small. So work done by the solid is

Let be the latent heat of fusion. It represents the heat needed per unit mass
to change from solid to liquid phase at constant temperature and pressure.

Then the amount of heat required for fusion of mass of a solid will be

Let and be the initial and final values of internal energy. According to
the first law of thermodynamics,

Or

7. CARNOT CYCLE:-

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 NET WORK DONE BY THE GAS PER CYCLE:

Total work done by the gas

(in steps 1 and 2)
Total work done on the gas
(in steps 3 and 4)
Net work done by the gas in one complete cycle,
( )
But

Also,

area area area area

Or

EFFICIENCY OF CARNOT ENGINE:

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It is defined as the ratio of the net work done per cycle by the engine to the
amount of heat absorbed per cycle by the working substance from the source.

Or
( )

( )

Now from ( ) to ( ) it is an adiabatic process, therefore

( )

Similarly, from( ) to ( ) it is again an adiabatic process,

therefore
( )

On dividing (1) and (2), we get

( ) ( )

Hence

8. CARNOT THEOREM:-

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Consider two engines – an irreversible engine and a reversible engine . The
two engines are so coupled that as runs forwards, it drives backwards. So
works as a refrigerator driven by .

The engine absorbs heat from the source, performs work and rejects
heat to the sink.

Efficiency of engine ,

The engine absorbs heat from the sink, work is done on it and it
rejects heat to the source.

Efficiency of engine ,

Suppose the engine is more efficient than . Then

or

i.e. is positive

The source loses heat to and gains from .

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 Net heat gained by the source per cycle

The sink gains heat ( ) from and loses to .

Net heat lost by the sink per cycle

( )

( )

The compound engine is a self – acting machine which transfers heat

( ) from the sink at lower temperature to the source at higher
temperature , without any work being done by any external agency.

This is against the second law of thermodynamics. So our assumption that is

more efficient than is wrong.

Hence no engine can have efficiency greater than that of the Carnot engine.

9. COEFFICIENT OF PERFORMANCE:-

It may be defined as the ratio of the amount of heat removed ( ) per cycle
to the mechanical work ( ) required to be done on it.

By first law of thermodynamics (energy conservation), the heat released to

the hot reservoir is

And
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 [ ]

Or

( )
Or

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