THERMAL SCIENCE

MEC 189.2
Sandip Thakur
Nepal Engineering College
Changunarayan, Bhaktapur

Second Law of Thermodynamics

Why Second Law of Thermodynamics?
First law of thermodynamics explains thermodynamic processes
with reference to mass conservation and energy conservation.

It deals with the quantitative aspect of the energy and gives the
only condition that any process is possible provided that the total
energy remains constant.
But some processes in nature cannot occur although energy
conservation principle is satisfied.

In this regard, second law of thermodynamics deals with quality or

nature of energy and defines the direction of the process in which
the system can proceed.

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Example 1
According the first law of thermodynamics, for a cyclic process net
heat transfer is equal to net work transfer.
But any real device, even operating on a cycle, cannot convert heat
supplied to it completely into output work.

Hence, the second law of thermodynamics explains why any real

engine cannot operate without heat loss.
Example 2

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Example 3
Work always produces some heat itself. But the reverse process i.e.,
the self conversion of heat to work (without any device) cannot
occur.
The second and third examples discussed above present the basic
nature or inherent tendency of a system (or a process); that most of
the processes in nature proceed in only direction. Such directional
feature of the processes cannot be explained only with the first law
of thermodynamics.
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Entropy
The main feature of the second law of thermodynamics is that it
defines the directions of the processes. Second law of
thermodynamics defines the direction of the process with reference
to the system property called entropy.
• System itself tends to undergo a process from less uncertain or
less random state to more uncertain or more random state. But
the reverse direction is not possible.

• High grade of energy (work) itself get converted into low grade
of energy (heat) and the reverse direction is not possible (without
any device)
The property of a system which gives a measure of molecular
randomness, disorder or uncertainty existing in a system is called
entropy. It is an extensive property and is denoted by S.
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Second Law of Thermodynamics for an Isolated System
Any isolated system can proceed in the direction in which its
randomness or uncertainty i.e., entropy increases.
This feature of the isolated system can be stated as the second law
of thermodynamics as

Entropy of an isolated system always increases or may remain

constant (in an ideal process).

The difference between entropies at the final state and the initial
state during any process is called entropy production or entropy
generation and is denoted by Sgen.
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We can rewrite the above Equation in equivalent from to avoid
inequality sign as

Reversible and Irreversible Processes

According to second law of thermodynamics, during any real
process net entropy change is always greater than or equal to zero,
i.e, for any process between state 1 and state 2,
S2  S1
During any process if S2 = S1 ; the reverse process is also possible
because entropy is same for both forward and reverse direction.
Hence the process is called reversible process.
During any process, if S2 > S1, i.e., entropy increases in forward
direction, then the reverse direction is not possible because any real
process can not result in decrease in entropy. Hence the process is
called an irreversible process.
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A process is said to be a reversible process if the initial conditions
of both the system and surroundings can be restored by the reverse
action such that net change in entropy is zero for both forward and
reverse process.
A process is said to be an irreversible process, if the initial
conditions of both the system and surroundings cannot be restored
(certain effects are left either on the system or on the surroundings)
by the reverse action. In this case entropy of the system increases in
forward process and therefore reverse direction is not possible.

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Entropy Relations
Applying state postulate, we can determine the internal energy of a
system if its volume and entropy are given as
U = U (S,V)

The change in internal energy during any process is then given as

The first partial derivative is equal to the temperature and the

second partial derivative is equal to the negative of the pressure, i.e.,

Substituting T and P in the above Equation,

……… Gibbs Equation
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Rearranging Gibbs equation, we can get the expression for the
change in entropy as

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Isentropic Efficiency of Steady Flow Devices
The process occurring in any steady flow device will be isentropic if
it does not involve any kind of losses (frictional loss, heat loss, etc)
therefore isentropic process is an ideal process.
But the process occurring in any real device involves losses and the
real process differs from the idealized isentropic condition.
The performance of the real device is compared with the idealized
device (isentropic) with reference to isentropic efficiency.
Isentropic Efficiency of a Turbine
In case of work producing device real work is always less than the
isentropic work output because of losses.
Hence, the isentropic efficiency of a turbine is defined as the ratio of
work output from a real turbine and the work that would have been
produced when the turbine operates under isentropic condition, i.e.,

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Isentropic Efficiency of a Pump/Compressor
In case of work consuming device real work is always more than the
isentropic work input because we have to increase work input to
overcome the losses to get the same desired output effect.
Hence, the isentropic efficiency of a pump or compressor is defined
as the ratio of the work that would have been required when the
pump/compressor operates under isentropic condition to work
required for the real pump/compressor and, i.e.,

Isentropic Efficiency of a Nozzle

Similarly, the isentropic efficiency of a nozzle is defined as the ratio
of the kinetic energy of the fluid at the real nozzle exit to the kinetic
energy value at the exit of an isentropic nozzle for the same inlet
state and exit pressure, i.e.,
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 “Kelvin-Plank” statement:

• The Kelvin-Plank statement of the second law of

thermodynamic is states that
– “It is impossible to for any devise as heat engine that
operates on a cycle to receive heat from a single reservoir
and produce net amount of work”.
• This statement means that only part of total heat absorbed by
heat engine from a high temperature is converted to work, the
remaining heat must be rejected at a low temperature.

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 Continued…..

• The heat engine as shown in

fig.1is converting 100 % of
Impossible
heat into 100% work.
• This system is not satisfying
second law.
• So, this statement can be
also expressed as “No heat
engine has a 100 % of
thermal efficiency”.

Possible

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 “Clausius” statement

• Clausius statement of second law of thermodynamic is as

below
– “It is impossible to construct a device as heat pump that
operates in a cycle and produces no effect other than the
transfer of heat from lower temperature to higher
temperature body”.
• This statement means that heat cannot flow from cold body to
hot body without any work input.

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 Heat Source T1 Heat Source T1

Q1=100 kj

Q1=100 kj W=40 kj
(external Heat
No external work pump
Heat supplied)
pump work
supplied
Q2=60 kj

Q2=100 kj Heat sink T2

Heat sink T2

Possible
Impossible
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 Continued:

• The cop for 2 is 100/40=2.5.

• So, in other simple words this statement can be defined as
– “Heat cannot itself flow from a colder body to a hot
body”.

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 COMPARISON
Kelvin-Plank Statement
• It is applied to ‘Heat
Engine’.
• It is negative statement.
• It is based on experimental
observations and no
mathematical proof.
Clausius Statement
• It is applied to ‘Heat Pump’
and ‘Refrigeration’.
• It is also negative statement.
• It is based on experimental
observations and no
mathematical proof.
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 Note: Do Yourself

• Other derivations done in class

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