The Second Law of

Thermodynamics
ME 121 – General Thermodynamics
and Heat Transfer
by AAP
Recall that from the first law of thermodynamics, during
any cycle that a system undergoes, the cyclic integral of
the heat is equal to the cyclic integral of the work.

The first law, however, places no restrictions on the

direction of flow of heat and work.

For a cycle will occur only if both the first and second
laws of thermodynamics are satisfied.
A system that undergoes a cycle involving work and heat.

An example showing the impossibility of

completing a cycle by transferring heat from a low
temperature body to a high-temperature body.
These two examples lead us to a consideration of the heat engine
and the refrigerator, which is also referred to as a heat pump.

With the heat engine we can have a system that operates in a cycle
and performs net positive work and net positive heat transfer.

With the heat pump we can have a system that operates in a cycle
and has heat transferred to it from a low-temperature body and
heat transferred from it to a high-temperature body, though work
is required to do this.
Thermal efficiency is defined as:

Eq. 1

The efficiency is the ratio of output, the energy sought (work), to

input, the energy that costs (heat form high-temp. source).

The efficiency of a refrigerator is expressed in terms of the

coefficient of performance (COP), which we designate with the
symbol β.

Eq. 2
There are two classical statements of the second law, known as the
Kelvin–Planck statement and the Clausius statement.

The Kelvin–Planck statement: It is impossible to construct a device

that will operate in a cycle and produce no effect other than the
raising of a weight and the exchange of heat with a single reservoir.
See Fig. 3.

The Kelvin–Planck statement.

The Clausius statement: It is impossible to construct a device that
operates in a cycle and produces no effect other than the transfer of
heat from a cooler body to a warmer body. See Fig. 4.

The Clausius statement.

A perpetual-motion machine of the first kind would create work from
nothing or create mass or energy, thus violating the first law.

A perpetual-motion machine of the second kind would extract heat

from a source and then convert this heat completely into other forms
of energy, thus violating the second law.

A perpetual-motion machine of the third kind would have no friction,

and thus would run indefinitely but produce no work.
THE CARNOT CYCLE
The most efficient cycle that can operate between two constant-
temperature reservoirs is called the Carnot cycle and is named after a
French engineer, Nicolas Leonard Sadi Carnot (1796–1832), who
expressed the foundations of the second law of thermodynamics in
1824.

It is impossible to construct an engine that operates between two

given reservoirs and is more efficient than a reversible engine
operating between the same two reservoirs.

All engines that operate on the Carnot cycle between two given
constant-temperature reservoirs have the same efficiency.
The efficiency of a Carnot cycle is independent of the working
substance and depends only on the reservoir temperatures.

Since the efficiency of a Carnot cycle is a function only of the

temperature, it follows that

Eq. 3

For simplicity, the thermodynamic scale is defined as

Eq. 4

Relationship between Carnot cycle efficiency and absolute

temperatures of two reservoirs

Eq. 5
Entropy
Inequality of Clausius, which is

Eq. 6

Entropy is an extensive property designated as S, and the entropy

per unit mass is designated s.
It may be defined as a property of a substance in accordance with
the relation

Eq. 7

The change in the entropy of a system as it undergoes a change of

state may be found by integrating Eq. 7. Thus,

Eq. 8
Note: Since entropy is a property, the change in the entropy of a
substance in going from one state to another is the same for all
processes, both reversible and irreversible, between these two states.

In the saturation region the entropy may be calculated using the

quality. The relations are similar to those for specific volume, internal
energy and enthalpy.

The two forms of the thermodynamic property relation and are

frequently called Gibbs equations. (simple compressible substance)
Eq. 9
Eq. 10
ENTROPY CHANGE OF AN IDEAL GAS
For an ideal gas

Therefore,
Eq. 11

Eq. 12

Also,

Therefore,
Eq. 13

Eq. 14
Assuming that the specific heats are constants, then eqs. 12 and 14
can be easily integrated and expressed as follows:

Eq. 15

Eq. 16

THE REVERSIBLE POLYTROPIC PROCESS FOR AN

IDEAL GAS

A process having this relation between pressure and volume is called

a polytropic process.

If n is a constant
Eq. 17
From eq. 17, the following relations can be written for a polytropic
process:

Eq. 18

For a control mass consisting of an ideal gas, the work done at the
moving boundary during a reversible polytropic process can be
derived. Recall:

for any
value of n Eq. 19
except
n = 1.
The values of n for some familiar processes are:

Isobaric process: n = 0, P = constant

Isothermal process: n = 1, T = constant
Isentropic process: n = k, s = constant
Isochoric process: n = ∞, v = constant
ENTROPY CHANGE OF A CONTROL MASS DURING AN
IRREVERSIBLE PROCESS

Consider a control mass that undergoes the cycles shown in the fig..
The cycle made up of the reversible processes A and B is a
reversible cycle. Therefore, we can write

The cycle made up of the irreversible process C and the reversible

process B is an irreversible cycle. Therefore, for this cycle the
inequality of Clausius may be applied, giving the result
Subtracting the second equation from the first and rearranging, we
have

Since path A is reversible, and since entropy is a property,

Therefore,

Entropy change of a control

mass during an irreversible
process.
As path C was arbitrary, the general result is

Eq. 20

In these equations the equality holds for a reversible process and the
inequality for an irreversible process.

In a reversible process, the If any irreversible effects

change of entropy is given by occur, the change of entropy
the relation will be greater than for the
reversible process.
ENTROPY GENERATION AND THE ENTROPY EQUATION

The amount of entropy generation in the process due to

irreversibilities occurring inside the system.
The entropy balance equation for a control mass in the same form as
the energy equation can be written in the general form

For example, state 1-2:

Eq. 21

Or if expressed as a rate equation:

Eq. 22
Some important conclusions:
•First, there are two ways in which the entropy of a system can be
increased—by transferring heat to it and by having an irreversible
process.
•Second, as we have already noted for an adiabatic process, δQ = 0,
and therefore the increase in entropy is always associated with the
irreversibilities.
•Third, the presence of irreversibilities will cause the work to be
smaller than the reversible work.
•Finally, it should be emphasized that the change in s associated with
the heat transfer is a transfer across the control surface, so a gain for
the control volume is accompanied by a loss of the same magnitude
outside the control volume.
Second-Law Analysis for a Control Volume
Steady-State Process - no change with time of the entropy per unit
mass at any point within the control volume.
The balance of entropy equation:
Eq. 23
so that, for the steady-state process,
Eq. 24

Eq. 25

in which the various mass flows, heat transfer and entropy

generation rates, and states are all constant with time.
If there is only one area over which mass enters the control volume at
a uniform rate and only one area over which mass leaves the control
volume at a uniform rate, we can write
Eq. 26

and dividing the mass flow rate out gives

Eq. 27
For an adiabatic process Eq. 28
where the equality holds for a reversible adiabatic process.
The shaft work for a single flow going through an actual process:

Eq. 29
For a reversible, steady-state process with no changes in kinetic or
potential energy and often also adiabatic, Eq. 29 reduces to

Eq. 30
Shaft work involved in this type of process is closely related to the
specific volume of the fluid during the process.
A simplified version of Eq. 29 arises when we consider a reversible
flow of an incompressible fluid (v = constant). The first integral is
then readily done to give
Eq. 31
which is called the extended Bernoulli equation after Daniel
Bernoulli, who wrote the equation for the zero work term, which
then can be written
Eq. 32
For reversible polytropic process for an ideal gas, we have the relations:

Eq. 33
If the process is isothermal, then n = 1 and the integral becomes
Eq. 34

Entropy change for a

control volume plus its
surroundings.
The entropy balance equation for the two control volumes:
Eq. 35

Eq. 36
The net rate of change of S for the total world:

Eq. 37
Example 1: An inventor claims to have developed a power cycle
capable of delivering a net work output of 410 kJ for an energy input
by heat transfer of 1000 kJ. The system undergoing the cycle receives
the heat transfer from hot gases at a temperature of 500 K and
discharges energy by heat transfer to the atmosphere at 300 K.
Evaluate this claim.

SOLUTION: Recall:

Then the maximum thermal efficiency any

power cycle while operating between
reservoirs:

Therefore, since the thermal efficiency of the

actual cycle exceeds the maximum theoretical
value, the claim cannot be valid.
Example 2:

SOLUTION:

The coefficient of performance of the refrigerator is:

The coefficient of performance of a reversible

refrigeration cycle operating between reservoirs:

Therefore, the difference between the actual

and maximum coefficients of performance
suggests that there may be some potential for
improving the thermodynamic performance.
Example 3:

SOLUTION:
From the definition of a heat engine efficiency, and the conversion of hp:

The energy equation for the overall engine gives:

From the energy release in the burning we have

Therefore, the rate of fuel consumption:

Example 4:

SOLUTION:
The variation in s follows from
From the fact that it is a Carnot cycle the COP becomes:

Notice how much the pressure varies during the heat rejection process. Because
this process is very difficult to accomplish in a real device, no heat pump or
refrigerator is designed to attempt to approach a Carnot cycle.
Example 5:

SOLUTION:
C.V. The refrigerant R-410a, which is a control mass, and in this case
changes in kinetic and potential energies are negligible.
Continuity Eq. Entropy Eq.
Energy Eq.
Process: T = constant, reversible, so equal sign applies in entropy equation
State 1:
State 2:

As T is constant, we have so from the entropy equation:

The work is then, from the energy equation,

Example 6:

SOLUTION:
Since the process is steady state, reversible, and adiabatic, and
because changes in kinetic and potential energies can be
neglected, we have

From the steam tables

Assuming that the specific volume remains constant.

Therefore, the work per kilogram to pump water is

Example 7:

SOLUTION:
From the energy equation we have
The second law gives us

From steam tables

Introducing the standard entropy:

The entropy change between any two states 1 and 2 is then given by
Therefore,

Example 8:

SOLUTION:

The boundary movement work is given by:

The first law is

Recall that for a polytropic process:

and from the energy equation,

Example 9:

SOLUTION:
For the control mass (water), from the steam tables, we obtain

Concerning the surroundings, we have

The decrease in the entropy of the water is equal to the increase in the
entropy of the surroundings.
Example 10:

SOLUTION:

The continuity equation gives us

From the energy equation we have

and the second law is

From the steam tables, we get
The two properties known in the final state are pressure and entropy:

The quality and enthalpy of the steam leaving the turbine can be determined as
follows:

Therefore, the work per kilogram of steam for this isentropic process is found
using the energy equation:
Example 11:

SOLUTION:
Because this is a steady-state process in which the work, heat transfer, and
changes in potential energy are zero, we can write

From the steam tables, we have

The two properties that we know in the final state are entropy and pressure:
Therefore,

Substituting into the energy equation, we have

Example 12:

SOLUTION:
Because this is a steady-state adiabatic process, we can write the second law
as

From the R-134a tables, we read

Therefore, , implying a negative entropy generation that is a violation

of the second law and thus is impossible.
Example 13:

SOLUTION:

Continuity Eq.
Energy Eq.
Entropy Eq.
Process:

All the states are specified (approximate state 2 with saturated liquid at 20◦C)
Now we can solve for the flow rate from the energy eq. and continuity eq.

Generation is from the entropy equation

Example 14:

SOLUTION:
For this single steady-state flow, we have no work or heat transfer, and
since it is incompressible and reversible, the Bernoulli equation applies,
giving

and the exit kinetic energy becomes

We can now solve for the velocity using a value of

Notice the factor of 1000 used to convert from kPa to Pa for proper units.
Example 15:

SOLUTION:
The efficiency, which is 85%, is given by

The energy equation for the real, irreversible process is

For the ideal, isentropic process from the energy equation is

and the second law is

Note that this equation is only for the ideal isentropic process and not for the real
process, for which

From the air tables

From the air tables at 830 K (the actual turbine exit temperature)
Therefore, from the energy equation for the real process,

Using the definition of turbine efficiency

From the energy equation for the isentropic process,

so that, from the air tables,

and the turbine inlet pressure is determined from

Second Exam:
Nov. 25, 2018
(Sunday)
12:00-3:00 pm
Amphitheater