CYCLIC PROCESS (NUMERICALS):

Q. One mole of an ideal gas undergoes a cyclic. change ABCD. From

the given diagram, calculate the net work done in the process.
1 atm = 106 dyne cm-2.

Solution:

Q. The P-V diagram, for a cyclic process is a triangle ABC drawn in order. The
coordinates of A, B, C are ( 4 , 1), (2, 4) and (2, 1).The coordinates are in the
order P, V. Pressure is in Nm-2 and volume is in litre. Calculate the work done
during the process from A to B, B to C and C to A. Also calculate the work done
in the complete cycle.
Solution:
FIRST LAW OF THERMODYNAMICS: If some heat is supplied to a
system which is capable of doing work, then the quantity of heat
absorbed by the system will be equal to the sum of the increase in its
internal energy and the external work done by the system on the
surroundings.

∆Q = Heat supplied to the system by the surroundings

∆W= Work done by the system on the surroundings

∆U = Change in internal energy of the system

∆Q=∆U + ∆W

THE WORK DONE BY THE SYSTEM AGAINST A CONSTANT PRESSURE:

∆W =Force x Distance

= Pressure x Area x Distance

=P A dx

Or, ∆W= P∆ V

So, the first law of thermodynamics takes the form,

 SPECIFIC HEATS OF GAS: When a gas is heated, its volume and
pressure change with the increase in temperature. So, the amount of
heat required to raise the temperature of 1 gram of gas through 1°C is
not fixed. That is a gas does not possess a unique or single specific
heat. A gas can have any value of specific heat depending on the
conditions under which it is heated.

LIMITS OF SPECIFIC HEAT OF GAS

1. Suppose the gas is suddenly compressed. No heat is supplied to

the gas i.e., ∆Q = 0. But the temperature of the gas rises due to
compression. specific heat of the gas is zero.

2. Now the gas is heated and allowed to expand such that the rise
in temperature of the gas due to the heat supplied is equal to
the fall in temperature of the gas due to the expansion of the
gas itself. Then the net rise in temperature is zero i.e., ∆T=0. The
specific heat of the gas is infinite.

3. Again, the gas is heated and allowed to expand at such a rate

that the fall in temperature due to expansion is less than the rise
in temperature due to heat supplied. The temperature of the gas
will rise i.e., ∆T is positive. specific heat of the gas is positive.

4. Finally, the gas is heated and allowed to expand at such a rate

that the fall in temperature due to expansion is more than the
rise in temperature due to heat supplied. The temperature of
gas will decrease i.e., ∆T is negative. Specific heat of the gas is
negative.
TWO PRINCIPAL SPECIFIC HEATS OF A GAS

One when the gas is heated at constant volume and another when the
gas is heated at constant pressure.

Molar specific heat at constant volume: It is defined as the amount of

heat required to raise the temperature of 1 mole of a gas through 1°C
at constant volume. It is denoted by CV.

Molar specific heat at constant pressure: It is defined as the amount

of heat required to raise the temperature of 1 mole of a gas through
1°C at constant pressure. It is denoted by CP.

CP is greater than CV.

The difference between the two specific heats is equal to the amount
of heat equivalent to the work performed by the gas during expansion
at constant pressure.

SPECIFIC HEAT RELATION: MAYER'S FORMULA

THERMODYNAMIC PROCESSES: A thermodynamic process is said to
occur if the thermodynamic variables of a system undergo a change
with time.

ISOTHERMAL PROCESS: An isothermal process is one in which the

pressure and volume of the system change but· temperature remains
constant
Consider an ideal gas enclosed in a cylinder provided with a piston
and having conducting walls. If the gas is slowly compressed, the heat
produced due to the work done on the gas is transferred to the
surroundings so that temperature of the gas remains constant.

Similarly, when the gas is allowed to expand slowly, its temperature

tends to fall but some heat from the surroundings is conducted to the
gas, keeping the temperature constant.

Essential conditions for an isothermal process to take place:

1. The walls of the container must be perfectly conducting to allow

free exchange of heat between the system and the
surroundings.

2. The· process of compression or expansion should be very slow,

so as to provide sufficient time for the exchange of heat.

FIRST LAW OF THERMODYNAMICS APPLIED TO ISOTHERMAL PROCESS

The internal energy of an ideal gas depends only on its temperature.

As temperature remains constant in an isothermal process, there is no
change in internal energy of the gas i.e.,∆U=0.
 I. When a gas, expands isothermally, ∆V and hence P ∆V is positive
and so ∆Q will also be positive. Therefore, when a gas expands
isothermally, an amount of heat equivalent to the work done the
gas has to be supplied from an external source.

II. When a gas is compressed isothermally, ∆V and hence P ∆V is

negative and ∆Q will also be negative. Therefore, when a gas is
compressed isothermally, an amount of heat equivalent to the
work done on the gas has to be removed from the gas.

III. In an isothermal expansion or compression, the internal energy

of the gas remains unchanged.

WORK DONE IN AN ISOTHERMAL PROCESS

. Consider is done by the gas during its n moles of an ideal gas

contained in a cylinder having conducting walls and provided with
frictionless and movable piston, as shown in the figure, let P be the
pressure of the gas.

Work done by the gas when the piston moves up through a small
distance dx is given by dW = PA dx = PdV

Where A is the cross-sectional area and dv = Adx, is the small increase

in the volume of the gas. Suppose the expands isothermally from
initial state (P1, V1 ) to the final state (P2, V2) The total amount of work
done will be
ADIABATIC PROCESS: An adiabatic process is one in which the
pressure, volume and temperature of the system change but there is
no exchange of heat between the system and surroundings.

when the gas is suddenly compressed, work is done on the gas. This
increases the internal energy of the gas. As heat cannot escape to the
surroundings, the temperature of the gas increases.

ESSENTIAL CONDITIONS FOR AN ADIABATIC PROCESS TO TAKE PLACE:

I. The walls of the container must be perfectly insulated so that

there cannot be any exchange of heat between the gas and the
surroundings.

II. The process of compression or expansion should be sudden, so

that heat does not get time to get exchanged with the
surroundings.

ADIABATIC RELATIONS BETWEEN P, V AND T

WORK DONE IN AN ADIABATIC PROCESS

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

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

dW = PA dx = P dV

where A is the cross-sectional area of the piston and dV = A dx is the

increase in the volume of the gas.

Suppose the gas expands adiabatically and changes from the initial
state (P1, V1, T1) to the final state (P2, V2, T2). The total work done by
the gas will be
when work is done by the gas during its adiabatic expansion, Wadia>0
and T2 < T1, i.e., temperature of the gas decreases. When work is done
on the gas during its adiabatic compression Wadia < 0 and T2 > T1 , i.e.,
temperature of the gas rises.

FIRST LAW OF THERMODYNAMICS APPLIED TO ISOCHORIC PROCESS

In an isochoric process, the volume V of the system remains constant.

As there is no change in volume (∆V =0), no work is done on or by the
system (W = P ∆V = 0). According to the first law of thermodynamics,

Hence, in an isochoric process, the entire heat given to or taken from

the system goes to change its internal energy and temperature of the
System. The change in temperature can be determined from the
equation

FIRST LAW OF THERMODYNAMICS APPLIED TO A CYCLIC PROCESS

In a cyclic process, the system returns to its initial state after

undergoing a series of changes. As internal energy is a state function,
so ∆U =0 for a cyclic process. From first law of thermodynamics,

Hence in a cyclic process, the total heat absorbed by a system is equal

to the work done by the system.

FIRST LAW OF THERMODYNAMIC APPLIED TO ISOBARIC PROCESS

A thermodynamic process which occurs at a constant pressure is

called an isobaric process. For example, freezing of water, formation
of steam, etc.

Suppose the pressure P of a gas remains constant and its volume

changes from V1 to V2, then the work done by the gas is

As the temperature of the gas changes, so its internal energy also

changes. Hence, in an isobaric process, the absorbed heat goes partly
to increase internal energy and partly to do work.
BOILING PROCESS: Suppose m mass of a liquid is heated at the
temperature of its boiling point so that it changes into vapour at a
pressure P. Let V be the volume of the liquid and VJ that of vapour. The
work done by the liquid during its expansion at temperature T is given
by

MELTING POINT: Suppose m mass of a solid is heated at its melting

point. When the solid melts, the change in its volume ∆V is negligibly
small. So, work done by the solid is

HEAT ENGINE: - is a device which converts continuously heat energy

into mechanical energy in a cyclic process.

i) Source: it is a heat reservoir at higher temperature T1.it is

supposed to have infinite thermal capacity so that any amount of
heat can be drawn from it without changing its temperature.
 ii) Sink: it is a heat reservoir at a lower temperature T2. it has also
infinite thermal capacity so that any amt of heat can be added to it
without changing its temperature.
iii) Working substance: is any material which performs mechanical
work then heat is supplied to it.

WORKING: - in every cycle of operation, the working substance

absorbs a definite amt. Of heat Q1 from the source at higher temp T1,
converts a part of this energy into mechanical work W and rejects the
remaining heat Q2 to the sink at lower temp. T2. The work done W in a
cycle is transferred to the environment by some arrangement, eg .The
working substance may be in a cylinder with a moving piston that
transfers mechanical energy to the wheels of a vehicle via a shaft.

EFFICIENCY OF A HEAT ENGINE: defined as the ratio of the net work

done by the engine is one cycle to the amt. Of heat absorbed bu the
working substance from the source.

NOTE: Efficiency of heat engine is always less than unity.

TYPES OF HEAT ENGINES

i) External Combustion engine- heat needed for the working
substance is produced by burning the fuel outside the cylinder
and piston arrangement of the engine. A steam engine is an
external combustion engine.
ii) Internal Combustion engine- heat needed for the engine is
produced by burning the fuel inside the main cylinder. The petrol
and diesel engines are internal combustion engines.
LIMITATIONS OF THE FIRST LAW OF THERMODYNAMICS
1. it does not indicate the direction of transfer of heat.

2. it does not tell anything about the conditions under which heat can be
converted into mechanical work.

3. it does not indicate the extent to which heat can be converted into
mechanical work continuously.

SECOND LAW OF THERMODYNAMICS: - many processes in which

energy is conserved and yet they are never observed. The principle which
disallows such phenomena consistent with the first law of
thermodynamics.
It can be stated as follow:
i) Kelvin-Planck statement- it is impossible to construct an engine,
which will produce no effect other than extracting heat from a
reservoir and performing an equivalent amount of work.

ii) Clausius statement- impossible for a self-acting machine, unaided

by any external agency, to transfer eat from a body to another at
higher temperature.

SIGNIFICANCE OF SECOND LAW

• the efficiency of a heat engine can never be unity. Implies that heat
released to the cold reservoir can be made zero.
• coefficient of performance of a refrigerator can never be infinite.
Implies that the external work(w) can never be zero.

LIMITATIONS OF THE SECOND LAW OF

THERMODYNAMICS
1. cannot be proved directly. But validity has not been contradicted by any
machine designed so far.

2. applicable to cyclic process in which the system returns to its original

state after a complete cycle of changes.

3. makes no predictions as to what will happen under certain conditions

but simply states what will happen under a given set of conditions.
REVERSIBLE AND IRREVERSIBLE PROCESSES

Reversible process- any process which can be made to proceed in the

reverse direction by variation in its conditions such that any change
occurring in any part of the direct process is exactly reversed in the
corresponding part of reverse process is called a reversible process.
NECESSARY CONDITIONS FOR A REVERSIBLE PROCESS –
• process must be quasi-static. For this the process must be carried out
infinitesimally slowly so that the system remains in thermal and
mechanical equilibrium with the surroundings throughout.

• the dissipative forces such as viscosity, friction, inelasticity, etc.

Should be absent.

Irreversible process- Any process which cannot be retraced in the

reverse direction exactly is called an irreversible process.
Eg. Diffusion of gases, rusting of iron, etc.

CARNOT ENGINE: is an ideal reversible heat engine that operates

between two temp. T1 (source) and T2(sink). It was first conceived by a
French engineer, Sadi Carnot in1824. It operates through a series of two
isothermal and two adiabatic processes called Carnot cycle. It is a
theoretical heat engine with which the efficiency of practical engines is
compared.
i) Cylinder – this main part of engine has counting base and
insulating walls. It is fitted with an insulating and friction less
piston.
 ii) Source- it is a heat reservoir at a higher temperature T1from
which the engine draws heat. It is supposed that the souce has an
infinite thermal capacity and so any amount of heat can be drawn
from it without changing its temperature.

iii) Sink- it is a heat reservoir at a lower temperature T2 to which any

amount Of heat can be rejected by the engine. It as also infinite
thermal capacity and so any amount of heat can be added to it
without changing its temperature.
iv) Working substance- the working substance is an idal gas
contained in the cylinder.
v) Insulating Stand- when base of cylinders attached to the
insulating stand, the working substance gets isolated from the
surroundings.

CARNOT CYCLE
EFFICIENCY OF CARNOT ENGINE: 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.

CARNOT THEOREM
states that
i) no engine working between two temperatures can have efficiency
greater than that of the Carnot engine working between the sae two
temp.
ii) the efficiency of the Carnot engine is independent of the nature of
the working substance.

REFRIGERATOR OR HEAT PUMP

Refrigerator- is a Carnot’s heat engine working in the reverse direction.

In a refrigerator, the working substance absorbs an amt. Of heat Q2 from

the cold reservoir at temp. T2. An amt. Of work W is one on it by some
external agency and rejects a larger quantity of heat Q1to the source at
temperature T1 as shown in fig.

In domestic refrigerators, food and ice constitute the cold reservoir and the
surroundings act as hot reservoir. Work is done by an electric motor and
freon is used as working substance.

➔ Working substance is carried through a cycle of following steps-

1. gas is allowed to expand suddenly from high to low pressure. This cools
it and converts it into vapour-liquid mixture.
2. cold fluid is allowed to absorb heat Q2 isothermally from the cold
reservoir. This converts the mixture into vapour.
3. then the vapour is adiabatically compressed till it heats up to the
temperature of the surroundings.
4. finally the vapour is compressed isothermally in contact with the
surroundings. The vapour releases heat Q1 (=Q2+W) to the surroundings
and returns to the initial state. Here W is work done on the gas per cycle.
COEFFICIENT PERFORMANCE: it may be defined as the ration of
the amt of heat removed (Q2)) per cycle to the mechanical work (W)
required to be done on it.
Therefore, β= Q2 / W
by first law of thermodynamics, the heat released to the hot reservoir is