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,
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 a
n irreversible process.
• Since the entropy generation cannot be less than zero, t
here is only one way in which the entropy of a system ca
n be decreased, and that is to transfer heat from the sy
stem.
• For an adiabatic process, δQ = 0, and therefore the in
crease in entropy is always associated with the irrevers
ibilities.
• Finally, the presence of irreversibilities will cause th
e work to be smaller than the reversible work. This mean
s less work out in an expansion process and more work in
to the control mass (δW <0) in a compression process.
• In fact, in many situations we are not certain o
f the exact
state through which a system passes when it und
ergoes
an irreversible process.
• The work for an irreversible process (fig. 8.11
a) is not
equal to P dV, and the heat transfer is not e
 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 specifi
c cause of irreversible entropy generation, such that the net
entropy change could also be termed the total entropy gener
ation:

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

where the equality holds for reversible processes and the in

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