Principal of entropy increase

Figure 23.1
Refer to Figure 23.1. Let a system change from state 1 to state 2 by a reversible process A and return to
state 1 by another reversible process B. Then 1A2B1 is a reversible cycle. Therefore, the Clausius
inequality gives:
(23.1)
If the system is restored to the initial state 1 from state 2 by an irreversible process C, then 1A2C1 is an
irreversible cycle. Then the Clausius inequality gives:
(23.2)
Subtracting (23.2) from (23,1)
(23.3)
Since the process 2B1 is reversible
(23.4)
or,
(23.5)
This can be generalized as
(23.6)
Where the equality sign holds good for a reversible process and the inequality sign holds good for an
irreversible process.

Now let us apply the above results to evaluate the entropy of the universe when a system
interacts with the surroundings. Refer to Figure 23.2.

Figure 23.2
Let Temperature of the surroundings
Temperature of the system
and,
(23.7)
If the energy exchange takes place,

will be the energy transfer from the surroundings to

the system.
(23.8)
(23.9)
(23.10)

(23.11)
[since

So,
(23.12)
If the system is isolated, that is, when there is no interaction between the system and the
surroundings, then
(23.13)

Now let us redefine a system which includes our earlier system and its surroundings. Then
for an isolated system
Through generalization we can write for an isolated system

(23.14)

(23.15)
Examine the statement critically. For a reversible process it is equal to zero. For an irreversible process it
is greater than zero.
Similarly it is possible to write

. The equality sign holds good if the process undergone is

reversible; the inequality sign holds good if the process undergone is irreversible.
Clausius summarized these as:
Die Energie der Welt ist konstant.
Die Entropie der Welt strebt einem Maximum

This means:
The energy of the universe in constant (first law).
The entropy of the universe tends towards a maximum (second law)
Temperature Entropy Diagram

Entropy change of a system is given by

. During the reversible process, the energy transfer

as heat to the system from the surroundings is given by

(24.1)

Figure 24.1

Refer to figure 24.1. Here T and S are chosen as independent variables. The
curve. The first law of thermodynamics gives

is the area under the

. Also for a reversible process, we can

write,
(24.2)

and
Therefore,

(24.3)
For a cyclic process, the above equation reduces to
(24.4)
For a cyclic process, the above equation reduces to
For a cyclic process

represents the net heat interaction which is equal to the net work done by the

system. Hence the area enclosed by a cycle on a T S diagram represents the net work done by a system.
For a reversible adiabatic process, we know that
(24.5)
or,
(24.6)
or,
(24.7)
Hence a reversible adiabatic process is also called an isentropic process. On a T S diagram, the Carnot
cycle can be represented as shown in Fig 24.1. The area under the curve 1-2 represents the energy
absorbed as heat

by the system during the isothermal process. The area under the curve 3-4 is the

energy rejected as heat

by the system. The shaded area represents the net work done by the system.

We have already seen that the efficiency of a Carnot cycle operating between two thermal reservoirs at
temperatures T1and T2

is given by
(24.8)

This was derived assuming the working fluid to be an ideal gas. The advantage of T S diagram can be
realized by a presentation of the Carnot cycle on the T S diagram. Let the system change its entropy
from

to

during the isothermal expansion process 1-2. Then,

(24.9)

and,

(24.10)
and,

or,
(24.11)

This demonstrates the utility of T S diagram.

Second law analysis of a control volume
It was shown that the change in entropy of a system is given by
(24.12)

Where the equality sign holds good for the reversible processes and the inequality sign holds
for all irreversible processes. This can be expressed as
(24.13)
Where

represents entropy generation in the system and it cannot take a negative value.
for a reversible process.
for an irreversible process.

Consider a control volume through which material flows (Figure 24.2)

Figure 24.2
Let us identify a system such that its mass remains constant during a given process. At time t,

the system constitutes both the mass inside the control volume and the mass about the enter the
control volume during a small interval dt (that is, the mass occupying the region A). At time
(t+dt), the system is the mass inside the control volume as well as the mass in region B. During
the time interval dt, the system undergoes a change in configuration and receives energy as
heat

from the surroundings.

At time t, the entropy of the system

(24.14)
At time

, the entropy of the system

(24.15)

Then,
(24.16)

or,
(24.17)

or,
(24.18)

This can be rearranged as

(24.19)

In words:
The rate of accumulation of entropy = Rate of inflow of entropy
Rate of outflow of entropy + Rate of generation of entropy
Steady-state steady-flow processes
The above equation can be simplified if one assumes steady flow and steady state
conditions. Under these conditions, there is no change in the entropy of the control
volume with respect to time, that is

. The steady flow assumption implies

that

and that

is a constant. Then we can write,

(24.20)

or,
(24.21)

For an adiabatic process

therefore

. However, if the process is

reversible and adiabatic then

Summary
In this lecture we have shown that
The Carnot cycle on a T S diagram and identify the heat transfer at both the high
and low temperatures, and the work output from the cycle.
1-2, reversible isothermal heat transfer

area 1-2-B-A.

2-3, reversible adiabatic expansion isentropic process, S = constant

3-4, reversible isothermal heat transfer
4-1, reversible adiabatic compression isentropic process,
Net work,

.
area 3-4-a-B.

the area enclosed by 1-2-3-4, the shaded area.

We have also done a Second Law Analysis of the Flow processes (control volume
based method)

TdS Equations
For a closed system contaning a pure compressible substance undergoing a
reversible process.
(24.22)
or
(per unit mass)
This is the famous Gibbsian equation.
Eliminate du by using the definition of enthalpy

(24.23)

(24.24)
Thus,

Also,

Entropy change of an incompressible substance

For most liquids and all solids the density is not changed as pressure changes, that
is,

. Gibbsian equation states that,

incompressible substance

is a function of temperature only.

Therefore,
Integrate to determine the entropy change during a process

, for an

where

is the averaged specific heat of the substance over the given temperature

range.
Specific heat for some common liquids and solids can be found in thermodynamic
tables.
Example Problem 2
An 1-kg metal bar initially at 1000 K is removed from an oven and quenched by
immersing in a closed tank containing 20 kg of water initially at 300 K. Assume both
substance are incompressible and c (water) = 4 (kJ/kg K), c (metal) = 0.4 (kJ/kg K).
Neglect heat transfer between the tank and its surroundings. (a) Determine the final
temperature of the metal bar, (b) entropy generation during the process.
Available Energy
In order to determine that part of the energy which can be converted into work by an
engine, we require consider a thermal reservoir at constant temperature T from which
a quantity of energyQ is being absorbed as heat.
A Carnot engine may be operated between the reservoir at T and the surroundings at
temperature T0 to convert part of the energy into work. The amount or work that can
be obtained is given by

(25.1)
Where

is the change in the entropy of the reservoir that supplies the energy. The

Carnot cycle is shown on a

diagram (Figure 25.1)

Figure 25.1
The area 1234 represents the portion of energy delivered as work by the reversible
engine and is called available energy .
The area 43BA represents the portion of the energy which is rejected to the
atmosphere.
The portion of energy is not available for conversion into work is called unavailable
energy . Therefore, the available energy represents the portion of the energy supplied
as heat which can be converted into work by means of a reversible engine. It is also
known as EXERGY .
The result

is true also for the case of a finite body, which acts as a

source, the temperature of which varies during the interaction.

Let us consider a finite body from which energy in the form of heat can be absorbed
by a heat engine. As the energy is with drawn from the finite body, the temperature of
the body keeps on decreasing. This process can be carried out using a large number of
differential Carnot engine. For a differential Carnot cycle, let

represent the

energy absorbed at temperature T. The differential amount of work done by the

engine is given by

(25.2)

Figure 25.2
If
the Carnot
engine Energy
works tilldue
the to
temperature
of the body
attains
a valueTemperature
(Figure
Loss
of Available
Heat Transfer
through
a Finite
Difference
Suppose a certain amount of energy Q is transferred as heat from a body at constant
temperature

to a body at constant temperature

Because of the finite temperature difference between the two interacting bodies, the
energy transfer is an irreversible process. This irreversibility leads to a loss in the
available energy. This loss in the available energy would not have occurred, had a
reversible engine been employed to transfer the energy from the body at
body at

to the

Suppose the same quantity of energy Q is absorbed by a reversible engine. Before the
energy transfer takes place the energy is available at temperature
transfer the energy is available at a lower temperature

. After the energy

. Let the ambient be at a

temperature

.
(25.4)

Then the initial available energy

(25.5)
the final available energy
Therefore the loss of available energy
(25.6)
(25.7)

Where
whenever

is the change in the entropy of the universe. It implies that

, there is a loss in the available energy.

The second law of thermodynamics states that,

, where the equality is

true for reversible processes and the inequality is true for all Spontaneous or
irreversible processes. Therefore, all spontaneous or irreversible processes are
associated with a loss of available energy.
Note that though the same amount of energy as heat is available before and after the
irreversible energy transfer, the available energy is less at
available energy at

compared to the

. That is, there is a degradation in the quality of the energy. The

internal energy at lower temperature is considered as degraded energy. We have seen

that all the energy absorbed as heat cannot be converted into work. That is, the
internal energy of a reservoir or a body is a low quantity energy.
On the other hand, work is considered as the highest quality of energy, because it is
interchangeable

to

the

other

forms

with hundred

percent

energy

conversion efficiency. It is possible to convert work completely into internal

energy, but not vice-versa .
The entropy generation associated with a heat transfer process can be well explained
by Figure 25.3 (a) and (b).

Figure 25.3

In Figure 25.3 (a) the presence of a well is ignored. The quantity

signifies entropy

transfer.
It is clear from both the cases, that whenever energy is transferred through a finite
temperature difference, entropy generation is brought about. Entropy generation is an
obvious outcome of an Irreversible process.
Availabilty Function and Irreversibility

Availability Function for a non-flow Process

Let the ambient pressure be

and the temperature be

. Since the system comes

toequilibrium with the ambient conditions, its final pressure is

. Let

and

represent the initial and final volumes of system respectively. Then the change in
volume of the system is
(26.1)
This change in volume of the system is resisted by the ambient pressure

. Then the

work done in pushing back the ambient pressure is.

(26.2)
Hence the useful work that can be obtained from the system is the maximum
work less the work done in pushing back the ambient atmosphere. Then
(26.3)
Availability =
To determine the availability of a system, let us consider a system which interacts
with the ambient at
We can write

or
or
Now,

(26.10)
The

second

law

of

thermodynamics

applied

to

the

control

volume

for reversible process gives

or
(26.11)
From (26.10) and (26.11)
(26.12)
or
Example
In a desalination plant, drinking water is produced by condensing steam in a heat
exchanger. Steam at 0.1 MPa and 150 0C enters the heat exchanger. Shown in fig at
the rate of 10000 kg/h and emerges as a liquid at 40 0C. Cooling water enters the heat
exchanger at 250C and leaves at 350C. Estimate the loss in availability in the heat
exchange process. The ambient temperature is 300K

Figure 26.1
First law:
= 2775.8 kJ/ kg ---------------

= 7.5984 kJ/ kg K

= 167.45 kJ/ kg ---------------

= 0.5721 kJ/ kg K

= 104.77 kJ/ kg ---------------

= 0.3670 kJ/ kg K

= 146.56 kJ/ kg --------------104 (2775.8) +

= 0.5049 kJ/ kg K

(104.77) = 10 4 (167.45) +

or
Change in availability of system

Change in availability of cooling water

(146.56)