M.N.

Sharath kumar

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Thermodynamics
It is a branch of physics which deals with the transformation of heat into other forms & vice-
versa. It deals with the transformation of energy.
Thermodynamic system: It is any physical quantity under consideration. It may be a solid, liquid
or gas or a combination also.
Thermodynamic variables: The physical quantities such as pressure, temperature & volume of a
system are variables.
Thermodynamic state: It is determined by variables.
Thermodynamic equilibrium: It is a state of a system in which thermodynamic variables have
unique values. If the system is in chemical, thermal & mechanical equilibrium then it is said to
be in thermodynamic equilibrium.
Zeroth law of thermodynamics: When the thermodynamic systems A & B are separately in
equilibrium with a third thermodynamic system C, then the systems A & B are also in thermal
equilibrium with each other.
Here the systems should be in thermal equilibrium with one another must have a
common temperature.
Internal energy: It is the total energy possesses by the system due to the molecular motion &
its configuration.
It is the sum o kinetic & potential energies of the molecules in a system.
i.e
k p
U U U = + ,
k
U is the total K.E.

p
U is the total P.E
U is the total energy.
For an ideal gas, intermolecular forces are zero. Thus
p
U 0 = .
So the total energy is nothing but the K.E of the system.
First law of thermodynamics:When a quantity of heat(Q) is supplied to a system, then the
quantity of heat absorbed by the system(Q) is equal to the sum of the increase in its internal
energy(Au) and the external work done by the system(W) against expansion.
Q u W = +
Q amount of heat supplied to the system.

2 1
u u u = i.e change in its internal energy
W it is the work done by the system.
This law is nothing but the law of conservation of energy.
Internal energy can be increased by
1) Supplying heat to system.
2) Doing external work on the system.
Sign convention:
1) When heat is absorbed by the system, Q is taken positive & when heat is liberated by
the system Q is taken negative.
2) When a gas expands, work is done by the gas so W is taken positive & when a gas
compresses, work is said to be done on the gas, W is negative.
Phase diagram:
Under suitable conditions of temperature and pressure matter can exist in 2 or more forms
simultaneously.

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For example at o c water exists in its liquid as well
as in solid form also at 100 c it exist in both liquid &
vapour form.
To discuss these stages we use phase diagrams. In this
pressure is plotted in y-axis & temperature in x-axis.
The above graph shows P-T diagram of water. Here the curve
PB gives the variation of melting point with pressure. PC
represents the sublimation line. Sublimation is a process in
which a substance directly changes from its solid to vapour
state under suitable temperature and pressure. The point `P`
is known as Tripple point.
For water, the triple point corresponds to the pressure of 4.58mm of Hg & 273.16k of
temperature.
Isothermal process: In an isothermal temperature remains constant. If the system is an ideal gas,
whose internal energy depends only on temperature, U remains constant u 0 = . From the first
law of thermodynamics
Q u W = +
Q W =
i.e heat supplied in an isothermal process is used to do work against the surroundings. Examples
are boiling of liquid, melting of wax etc.
Adiabatic process: In an adiabatic process, heat neither enters nor leaves the system i.e Q 0 = .
The first law of thermodynamics
Q u W = +
u W =
When a gas expands adiabatically, W is positive. So umust be negative i.e internal
energy of the system would decrease and the gas will be cooled. Some of the examples are
bursting of an automobile tube, propagation of sound waves in a gas etc.
Isochoric process: When the volume of a system is constant, W 0. From the first law of
thermodynamics
Q u W = +
Q u =
If heat is absorbed by a system at constant volume. Its internal energy increases.
Example: 1) Explosion of gas.
2) Melting of a solid into a liquid.
Isobaric process: In this pressure is kept constant. Since the volume can change the gas expands
& work is done. Thus in this process Au & W are both not zero.
Q u W = +
Examples:
1) Heat of a liquid.
2) Heating of gas at constant pressure.
Cyclic process: In this process, the system returns to its initial state after a number of changes.
In this case, the internal energy of the system wont change.
Au = 0
From the first law of thermodynamics
Q u W = +
T
p
Tripple point
A
B
p
C
pA vapourisation line
pB fusion line
pC sublimation line

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Q W =
Network during a cyclic process must be equal to the amount of heat energy
transferred.
Reversible process: It is a process which can be made to proceed in two opposite directions so
that the system and the surroundings pass through exactly the same intermediate states as in the
direct process.
In reversible process the total work done in bringing back the system to the initial state is
zero.
Irreversible process: It is a process which cannot be made to proceed in the reverse direction in
the same path & the system does not pass through the same intermediate states in the direct &
reverse processes.
This always involves loss of energy. This loss in energy is represented by the area of the
loop in the p-v diagram.
Heat engine: An heat engine is a device which converts heat energy into mechanical energy.
It consists of 3 parts.
1) Source: It is an agency which can provide any amount of heat. It is maintained at
constant temperature.
2) Working substance: It is an enclosed system which can do work.
3) Sink: Sink can absorb any amount of heat to maintain its temperature constant.
Temperature of sink is less than of source.
Principle: The working substance absorbs heat from the source & converts a part of it into work
& rejects the rest to the sink.
Let
1
Q = amount of heat absorbed by the working substance & from the source at
1
Tk.
W= total work done by the working substance.

2
Q = amount of heat rejected to the sink at
2
T k.
Net amount of heat absorbed is

1 2
Q Q Q (1) =
As the working substance returns to original state, change in internal energy u 0.
According to the first law of thermodynamics
Q u W = +
Q W (2) u 0 = =
From (1) we can write

1 2
W Q Q =
Efficiency: It is defined as the ratio of net work done per cycle by the engine to the total amount
of heat absorbed per cycle by the working substance from the source. It is denoted by q.

1 2
1 1
W Q Q
Q Q

q = =

2
1
Q
1
Q
q =

Types of heat engines:
There are two types of heat engines:
1) External combustion engine: In this fuel is burnt outside the main body o the engine.
Steam engine is an example.

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2) Internal combustion engine: In this fuel is burnt inside the main body of the engine.
Petrol & diesel engine are examples.
Carnots engine & Carnots cycle:
Construction: The parts are as shown:

Source
Insulator Sink
Ideal gas

Source: It is maintained at a fixed higher temperature
1
T from which working substance draws
heat.
Sink: It is maintained at constant temperature
2 2 1
T (T T ) < .
Working substance: A perfect gas acts as a working substance. It is contained in a chamber with
non-conducting side walls but perfectly conducting base. It is fitted with a piston which is
frictionless. The piston is a non-conductor.
Insulator: It is used to cover the entire base of the container. It ensures thermal isolation of the
working substance.
Note: Both Source & sink possess infinite thermal capacity i.e give or absorb infinite heat
within itself.
Theory: The carnots engine is taken through four process
1) Isothermal expansion:
In this, the base of the container is brought in contact with the source which is maintained
at temperature
1
T and the gas is allowed to undergo isothermal expansion. During the expansion,
it absorbs heat energy
1
Q from the source which is represented
by the curve AB is the p-v diagram.
The gas is taken from the state
1 1 1
A(PVT ) to
2 2 1
B(P VT ) .
2) Adiabatic expansion: Now the base is brought in contact with the insulator & the gas is
allowed to expand to attain the state
3 3 2
C(P VT ) . In this no energy flows into or from the
system. Adiabatic expansion is represented by the curve BC.
3) Isothermal compression: Her the base is brought in contact with the sink & the gas is
allowed to undergo compression at constant temperature
2
T to reach the state
4 4 2
D(P VT ) . This is represented by the curve CD.
4) Adiabatic compression: In this the base of the container is brought in contact with the
insulator & the gas is compressed back to state
1 1 1
A(PVT ) . This is represented by the
curve DA.
The curve ABCDA represents carnots cycle. During expansion, work is done by
the gas and during compression work is done on the gas. The total work done by the
working substance is given by the area enclosed by the loop ABCDA.
Efficiency of carnots engine:
Efficiency of a carnots engine is given by

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2
1
Q
1
Q
q =
It can be shown that
2 2
1 1
Q T
Q T
=

2
1
T
1
T
q =
Thus efficiency of the carnots engine depends only on the temperature of source & sink.
q= 1 when
2
T 0. This forms the basis for the definition of absolute temperature.
It is defined as that temperature of the sink for which the efficiency of a carnots engine
is 100%.
Claussius-clapeyron equation: The boiling point & melting point expressions in terms of pressure
is obtained by claussius-clapeyron equation. It is given by

2 1
dp L
dT T(V V)
=

L Latent heat of the substance
T boiling/melting point.

2 1
(V V) Change in volume.
Where dT is the change in boiling point or melting for a change in pressure dP.
Effect of pressure on boiling point: The claussius-clapeyron equation is

2 1
dp L
dT T(V V)
=

L is the latent heat of vapourisation, T is the boiling point of the liquid with change in
volume
2 1
(V V) . Here
2
V is always greater than V. So
2 1
(V V) is +ve so
dp
dT
is also
positive. The boiling point of a liquid increases with increase in pressure.
Effect of pressure on melting point: The claussius-clapeyron equation is given by

2 1
dp L
dT T(V V)
=

L is the latent heat of fusion of solid & T is the melting point.
Case 1: Volume may increase:
When wax melts, its volume increases i.e
2 1
V V > .
Therefore
2 1
(V V) is +ve so
dp
dT
. The melting point increases with increase in pressure.
Case 2: Volume may decrease:
When ice melts, its volume decreases i.e
1 2
V V > .
Therefore
2 1
(V V) is ve. In this, the melting point decreases with increase in pressure.
Second law of thermodynamics: This establishes the relation between heat and mechanical
energy. It is known that the total heat content of a body cannot be entirely converted into work
done. This behaviour is stated in the second law.
Kelvins statement:
It is impossible to obtain a continuous supply of work from a body by cooling it to a
temperature below the lowest of its surroundings.


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Claussius statement:
It is impossible for a self acting machine unaided by an external, to transfer heat from a
body at lower temperature to a body at higher temperature.
Application of second law of thermodynamics:
Refrigerator:


Source
Sink
WS
Work

It works on the principle of carnots heat engine but taken in a reverse order. It absorbs
an amount of heat
2
Q form the sink(freezer) at lower temperature
2
T and rejects to the source at
higher temperature
1
T . For this purpose, the compressor performs an amount of work
1 2
W Q Q = . The net amount of heat liberated to source is
1 2
Q W Q = + .
Co-efficient of performance: It is defined as the ratio of quantity of heat removed per cycle from
the refrigerator to the mechanical work done by the external agency to remove it. It is denoted
by |(Beta).

2
Amount of heat removed Q
work done W
| = =

2
1
1 2
2
Q 1
Q
Q Q
1
Q
= =

Wkt
1 1
2 2
Q T
Q T
=

1
2
1
T
1
T
| =

2
1 2
T
T T
| =

Usually | value varies from 2 to 6. In refrigerator we can see that the heat cannot be transferred
from a body at lower temperature to a body at higher temperature unless an external agency
help. This illustrates second law of thermodynamics.
Entropy: It is defined as that physical quantity which remains constant when the substance
undergoes a reversible adiabatic change. It is represented by S.

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Q
dS
T
=
Where dQ is the heat energy supplied to the system at temperature T.
Second law of thermodynamics can also be stated using entropy as follows.
If a process occurs in a closed system, the entropy of the system increases, for a
irreversible processes & remain constant for reversible processes.
Entropy of a system can never decrease. ds 0 >
Explanation of first law of thermodynamics:
1) This law is an illustration for conservation of energy.
2) In this law all the quantities i.e AQ, AV, AW must have the same unit.
3) This law is applicable for all processes in nature.
4) It is applicable for all 3 states of matter. i.e solid ,liquid & gases.
5) It gives the concept of internal energy.
6) From this, it is impossible to get work from any machine giving an amount of energy.