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Engineering Thermodynamics 1

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The Property of Entropy

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8.
8.1

Entropy
The Property Entropy

A corollary of the second law is the Clausius inequality that is applicable to


any cycle without regard for the body, or bodies from which the cycle
receives energy by heat transfer or to which the cycle rejects energy by
heat transfer.
The Clausius inequality states that for any thermodynamic cycle

Q
T

0
b

2
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Where Q represents the heat transfer at a part of the system


boundary during a portion of the cycle and T is the absolute
temperature at that part of the boundary. The subscript b serves as a
reminder that the integral is evaluated at the boundary of the system
executing the cycle. The symbol indicates that the integral is to be
performed over all parts of the boundary and over the entire cycle.
The equality and the inequality have the same interpretation as in the
Kelvin-Planck statement: the equality applies when there are no
internal irreversibilities as the system executes the cycle and the
inequality applies when internal irreversibilities are present.

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Recall
heat cannot by itself pass from a cold to a hot body. (Clausius)
Kelvin-Planck

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The suffix int. rev is added as a reminder that the relation only holds for
an internally reversible process. The unit of S is kJ/K and s is (kJ/kg.K).
Notice the parallelism between the definitions of E and S.

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The property entropy arises as a consequence of the second law in


much the same way as the property internal energy arises from the first
law. There is however an important difference, the change in internal
energy can be found directly from knowledge of the work and heat
transfer across the closed system boundary. The change in entropy on
the other hand can be found from knowledge of the quantity of heat
transferred only during a reversible process.

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As with internal energy only changes of entropy are of interest. The


entropy at an arbitrary state can be made zero and the entropy at any
other state can then be found by evaluating for any reversible process by
which the system can change from the reference state to the other state.
Since no real process is reversible, values of entropy cannot be found
from measurements of Q and T in a direct experiment.
Since entropy is a property, the change in entropy in going from one state
to another is the same for all processes, both internally reversible and
irreversible, between these two states.
.

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8.1.1 Isentropic Process


For any thermally insulated system dQ = 0. But for any reversible
process dS = dQ/T.
Therefore for any reversible adiabatic process, the change of
entropy must be equal to zero. For this reason a reversible
adiabatic process is called an isentropic process.

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8.2 Useful Relationships


Entropy is a thermodynamic property and it can be expressed as a
function of other thermodynamic properties which can be measured
by experiments involving real processes. This aids in the evaluation
of entropy values. Two important relationships of this kind can be
obtained by combining the first law and second laws.
The TdS equations are developed by considering a pure, simple
compressible system undergoing an internally reversible process.:

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Equations 4 and 5 are general relations between properties


which apply to any fluid. Moreover, when integrated they
give the differences in entropy between any two equilibrium
states regardless of whether any particular process joining
them is carried out reversibly or not.
On a per mass basis the equations are reduced to

Tds du pdv

Tds dh vdp
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Entropy change for an Ideal Gas


For an ideal gas, specific heats are functions of temperature only and the
pvT relationship is such that the second term on the right can be readily
integrated to give.

s 2 s1

cv dT
v2
R ln
T
v1

and

s 2 s1

c p dT
T

p2
R ln
p1

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8.3 Entropy as a coordinate


From the entropy relationship we have q = Tds for a closed system.
Therefore the heat transfer to/from the system during the reversible
process is represented by the area beneath the path 1-2 on a Ts
diagram.

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T-s and h-s diagrams for a pure substance is shown below

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A Carnot cycle is composed of two reversible isothermal


processes and two reversible adiabatic or isentropic
processes. Therefore a Carnot cycle is always represented
by a rectangle on a T-s diagram.

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It is important to note that the area beneath the path of an irreversible


process on a T-s diagram has no significance. It does not represent heat
transfer because Qirrev Tds

Irreversible processes are shown as broken lines on T-s


diagrams.

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8.4 The Increase of Entropy Principle


The property entropy provides a means of determining if a process is
possible and if so, whether it is reversible or irreversible. This is
accomplished using the increase of entropy principle: the entropy of
an isolated system always increases or, in the limiting case of a reversible
process, remains constant with respect to time.
In mathematical form,

dS

dt

or with the understanding that time is

isolatedsystem

the independent variable, this statement is usually written

S isolatedsystem 0 .

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The inequality holds for irreversible processes and the equality holds for
reversible processes. Note that for an isolated system the heat interaction
and work interactions outside the system boundary are zero.
The term isolated system is treated here as a single system comprising a
system together with its surroundings.
Another way of stating the principle is that: the entropy of an adiabatic
closed system always increases or, in the limiting case of a reversible
process remains constant. This statement is more general than stating an
isolated system since the latter includes W = 0 as a criteria. An isolated
system is a special case (W = 0)of an adiabatic closed system.
0

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For any process of an isolated system


If the entropy of the system remains constant, the process is
reversible. This occurs when the process is adiabatic. When the
process is not adiabatic, and
If the entropy of the system increases, the process is irreversible
The entropy of an isolated system cannot decrease. This criterion
demonstrates whether a process will occur or not.

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Consider the heating of a block of steel from a temperature T1 to a


temperature T2. Heat is supplied from a constant temperature reservoir at
TH. TH is greater than T2. Neither the block nor the reservoir is isolated, but
the block and the reservoir together constitute an isolated system. Since
the transfer of heat from the reservoir to the block across a finite
temperature difference is irreversible, the entropy of the isolated system
increases. This can be seen from the T-S diagrams below.

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Since the heating of the block and the cooling of the reservoir are
internally reversible because no dissipation of energy takes place within
the system, the amount of heat transferred is represented by the area
beneath the path of each TS diagram. The two areas must be equal (Q is
the same) so the lower temperature of the block requires that

S block S reservoir

and thus S isolatedsystem 0

Therefore the system must be irreversible.


Note, because the elements of the reservoir undergo only infinitesimal
changes, the process undergone by the reservoir as a whole when the
quantity of heat Q leaves must be considered reversible. It follows that
the entropy change of the reservoir is simply Q/TH.
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An isolated system can always be formed by including any system and


the surroundings with which it interacts with a single boundary.
Sometimes the original system which is then only a part of the isolated
system is called a subsystem. Since a system and its surroundings
include by definition everything that is affected by the process, the
combination is sometimes called the universe, so that the increase of
entropy principle is stated as:
Suniverse

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Where Suniverse = Ssystem + Ssurroundings

Notice that no conclusion has been drawn regarding S of a


system in general. The entropy of a system may increase,
decrease or remain constant. It is only the entropy of the universe
or of an isolated system that must increase or, in the case of a
reversible process, remain constant.
All real processes must occur is such a direction that the state of
the universe changes from one of lower to one of higher entropy.

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Recall that we define the surroundings as everything outside the


system boundary but usually restrict the term to things outside the
system that in some way affect the behaviour of the system.
Consequently the term universe generally refers to everything that is
involved in a process and need not include things that have no effect
on the process. The universe is thus an isolated system and its
entropy must either increase or remain constant.
Some possible adiabatic compression and expansion paths for
Reversible and irreversible processes on T-s coordinates are shown.

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