Second Law of

Thermodynamics
Week - 4 -
DASTAN KHALID
 Introduction
The first law of thermodynamics says that, in any process, energy is conserved. Energy may be
converted from one form to another, but the total amount of energy is unchanged.
The second law of thermodynamics imposes limits on the efficiency of processes that convert
heat into work, such as in a steam engine or internal combustion engine.
It allows for the definition of a thermodynamic temperature scale, which is independent of the
nature of the thermometric substance.
The second law also leads to the concept of entropy, which is related both to bulk processes and
to the microscopic arrangements within a system.
Before considering the second law, it is useful to discuss cycles, which are central to the
development of understanding the second law
Cycles
To develop our understanding of the second
law of thermodynamics, we need to first
discuss cycles and the properties of a cycle.

We have seen that for a given system we may

carry out several processes, where a given
process takes on a specific path.
A system is said to have undergone a cycle if it
returns to its initial state at the end of the
process. That is, for a cycle the initial and final
states are identical
Cycles
The energy balance for any system undergoing Depending on the system input and output,
a thermodynamic cycle takes the form we have two general classes of cycles which
we consider, these are

◦ power cycles
Since from the definition of cycle, the system ◦ refrigeration and heat pump cycles
is returned to its initial state, there is no net
change in its energy (∆𝐸𝑐𝑦𝑐𝑙𝑒 = 0)and
therefore the equation above becomes
Cycles
Carnot cycle
In a Carnot cycle, the system executing the cycle
undergoes a series of four internally reversible
processes: two adiabatic processes alternated
with two isothermal processes. Shown from the
figure is a Carnot cycle for a power cycle.
It provides an upper limit on the efficiency that
any classical thermodynamic engine can achieve
during the conversion of heat into work, or
conversely, the efficiency of a refrigeration system
in creating a temperature difference by the
application of work to the system.
It is not an actual thermodynamic cycle but is a
theoretical construct.
Power cycle
Systems undergoing cycles of the type shown in the
figure deliver a net work transfer of energy to their
surroundings during each cycle.
Any such cycle is called a power cycle.
From the figure and the definition of energy in a It is clear from the
cycle, we can express the work via
equation that Qin must
be larger that Qout for a
power cycle

where Qin represents the heat transfer of energy

into the system from the hot body, and Qout
represents heat transfer out of the system to the
cold body.
Power cycle – thermal efficiency
The performance of a system undergoing a power
cycle can be described in terms of the extent to
which the energy added by heat, Qin, is converted to
a net work output, Wcycle.
The extent of the energy conversion from heat to
work is expressed by the following ratio, commonly
called the thermal efficiency
Since energy is conserved, it follows that the
thermal efficiency can never be greater than unity
(100%).
However, experience with actual power cycles
shows that the value of thermal efficiency is
invariably less than unity.
This means, not all the energy added to the system
by heat transfer is converted to work; a portion is
discharged to the cold body by heat transfer.
Using the second law of thermodynamics, we will
show that the conversion from heat to work cannot
be fully accomplished by any power cycle.
The thermal efficiency of every power cycle must be
less than unity
Refrigeration
The next example on cycles we consider the refrigeration
and heat pump cycles shown the figure
For cycle of this type, Qin is the energy transferred by heat
into the system undergoing the cycle from the cold body,
and Qout is the energy discharged by heat transfer from
the system to the hot body.
To accomplish these energy transfers requires a net work
input, Wcycle.
The quantities Qin, Qout, and Wcycle are related by the
energy balance
Refrigeration cycle – thermal efficiency
The performance of refrigeration cycles can be
described as the ratio of the amount of energy
received by the system undergoing the cycle
from the cold body, Qin, to the net work into
the system to accomplish this effect, Wcycle.
Thus, the coefficient of performance, 𝛽, is
For a household refrigerator, Qout is discharged
to the space in which the refrigerator is
located.
Wcycle is usually provided in the form of
electricity to run the motor that drives the
refrigerator.
Heat pump cycle
The performance of heat pumps can be
described as the ratio of the amount of energy
discharged from the system undergoing the
cycle to the hot body, Qout, to the net work
into the system to accomplish this effect,
Wcycle.
Thus, the coefficient of performance,𝛾 , is
From this equation it can be seen that the
value of 𝛾 is never less than unity.
For residential heat pumps, the energy
quantity Qin is normally drawn from the
surrounding atmosphere, the ground, or a
nearby body of water. Wcycle is usually provided
by electricity.
Second law of thermodynamics
It is a matter of everyday
experience that there is a
definite direction for
spontaneous processes.
This can be brought out
by considering the three
systems pictured
Second law of thermodynamics
Our discussion indicates that not every process consistent with the principle of energy
conservation can occur.
Generally, an energy balance alone neither enables the preferred direction to be
predicted nor permits the processes that can occur to be distinguished from those that
cannot.
In elementary cases, such as the ones considered before, experience can be drawn upon
to deduce whether particular spontaneous processes occur and to deduce their
directions.
For more complex cases, where experience is lacking or uncertain, a guiding principle is
necessary.
This is provided by the second law.
 2nd law statement
Clausius Statement :
It is impossible for any system to
operate in such a way that the sole
result would be an energy transfer
by heat from a cooler to a hotter
body.
cooling of food is most commonly
accomplished by refrigerators driven
by electric motors requiring power
from their surroundings to operate.
The Clausius statement implies it is
impossible to construct a
refrigeration cycle that operates
without a power input.
2nd law statement
Kelvin–Planck Statement:
It is impossible for any system to operate in a
thermodynamic cycle and deliver a net
amount of energy by work to its surroundings
while receiving energy by heat transfer from
a single thermal reservoir.
2nd law statement
The entropy statement of the second law
states:
It is impossible for any system to operate in a
way that entropy is destroyed.
Just as mass and energy are accounted for by
mass and energy balances, respectively,
entropy is accounted for by an entropy
balance.
Second Law Aspects of Power Cycles
A significant limitation on the performance of systems undergoing power cycles can be brought
out using the Kelvin–Planck statement of the second law.
Consider the figure, which shows a system that executes a cycle while communicating thermally
with two thermal reservoirs, a hot reservoir and a cold reservoir, and developing net work Wcycle.
The thermal efficiency of the cycle is

Carnot
efficiency

because
Second Law Aspects of Refrigeration
and Heat Pump Cycles
The second law of thermodynamics places limits on the
performance of refrigeration and heat pump cycles as it
does for power cycles.
The energy transfers labelled on the figure are in the
directions indicated by the arrows.
In accord with the conservation of energy principle, the
cycle discharges energy QH by heat transfer to the hot
reservoir equal to the sum of the energy QC received by
heat transfer from the cold reservoir and the net work
input.
This cycle might be a refrigeration cycle or a heat pump
cycle, depending on whether its function is to remove
energy QC from the cold reservoir or deliver energy QH to
the hot reservoir.
Using Entropy – Clausius inequality
Before we apply the concept of entropy, we Definition of entropy
should know the mathematical definition of
Clausius Inequality which states for any cycle:

And the differential form of

Introducing entropy equation
The entropy equations are developed by Therefore the first law of thermodynamics can
considering a pure, simple compressible be written as
system undergoing an internally reversible
process. In the absence of overall system
motion and the effects of gravity, an energy
balance in differential form is
And for enthalpy equation we have

With
Statistical Interpretation of Entropy
Entropy Rate Balance for Control Volumes
Thus far the discussion of the entropy balance On a time rate basis, the closed system
concept has been restricted to the case of entropy rate balance is
closed systems.
For a closed system we had :

Finally, for a control volumes we have

For Tb being constant, we have

Rate Balances for Control Volumes at
Steady State
Remembering The energy rate balance at steady state was

Finally, the steady-state form of the entropy rate balance is obtained by

For one inlet – one exit system we have