Entropy

Chapter 8
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• The important point is that 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.
• From the third law of thermodynamics, which is based on
observations of low-temperature chemical reactions, it is
concluded that the entropy of all pure substances (in the
appropriate structural form) can be assigned the absolute value
of zero at the absolute zero of temperature. It also follows from
the subject of statistical thermodynamics that all pure
substances in the (hypothetical) ideal-gas state at absolute zero
temperature have zero entropy.
• However, when there is no change of composition, as would
occur in a chemical reaction, for example, it is quite adequate to
give values of entropy relative to some arbitrarily selected
reference state, such as was done earlier when tabulating
values of internal energy and enthalpy. In each case, whatever
reference value is chosen, it will cancel out when the change of
property is calculated between any two states.
 8.3 The Entropy of Pure Substance

• In the steam tables the entropy of saturated liquid at

0.01C is given the value of zero.
• For many refrigerants, the entropy of saturated liquid
at 400C is assigned the value of zero.
• 1/T serves as the integrating factor in converting the
inexact differential δQ to the exact differential δQ/T
for a reversible process.
8.4 ENTROPY CHANGE IN REVERSIBLE PROCESSES

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Net work
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Eq.6.13

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( Gibbs equations )
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2
2 - 1

0 + -
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8.7 ENTROPY GENERATION
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Some Important Conclusions
• 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.
• Since the entropy generation cannot be less than zero,
there is only one way in which the entropy of a
system can be decreased, and that is to transfer heat
from the system.
• For an adiabatic process, δQ = 0, and therefore the
increase in entropy is always associated with the
irreversibilities.
• Finally, the presence of irreversibilities will cause the
work to be smaller than the reversible work. This
means less work out in an expansion process and
more work into the control mass (δW <0) in a
compression process.
• In fact, in many situations we are not certain of the
exact
state through which a system passes when it
undergoes
an irreversible process.
• The work for an irreversible process (fig. 8.11a) is not
equal to P dV, and the heat transfer is not equal to T
dS.
 8.8

1 For the control mass

2
c.m.2
• Thus we conclude that the net entropy change is the sum of
a number of terms, each of which is positive, due to a
specific cause of irreversible entropy generation, such that
the net entropy change could also be termed the total
entropy generation:

dSnet =dScm +dSsurr = Σδ Sgen ≥ 0 --------- (8.16)

where the equality holds for reversible processes and the

inequality for irreversible processes.
8.9 ENTROPY CHANGE OF A SOLID OR LIQUID
8.10 ENTROPY CHANGE OF AN IDEAL GAS
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