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DownloadLecture 11 - Entropy Evaluation, Third Law

The document discusses the combined first and second law equations for closed systems undergoing internally reversible processes. It provides expressions for differential changes in entropy for solids, liquids, and ideal gases. The statistical and disorder interpretations of entropy are described. The third law of thermodynamics stating that the entropy of a pure crystalline substance at absolute zero is zero is also discussed.

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11 views

DownloadLecture 11 - Entropy Evaluation, Third Law

The document discusses the combined first and second law equations for closed systems undergoing internally reversible processes. It provides expressions for differential changes in entropy for solids, liquids, and ideal gases. The statistical and disorder interpretations of entropy are described. The third law of thermodynamics stating that the entropy of a pure crystalline substance at absolute zero is zero is also discussed.

Uploaded by

euglena6
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Lecture 11

Combined First and Second Law equations

First law for a closed system in the differential form for an internally reversible process
=

But
=

Therefore

= + kJ
Or

= + kJ/kg ..(1)
h = u + pv
dh = du + pdv + vdp
but
du + pdv = Tds according to eq (1)
Tds = dh vdp kJ/kg..(2)
Eq (1) and (2) are known as combined first and second law equations.
Relations for differential changes in entropy

Expressions for ds can be obtained by dividing eq 1 and 2 by T



=
+

(3)

And

= + (4)

Entropy changes for solids and liquids

Solids and liquids can be approximated as incompressible substances since their specific volume
remains nearly a constant during a process. Therfore dv0 for solids and liquids.

Eq (3) now becomes



= =

Integrating for a process 1-2

= kJ/kg

Where c is the average specific heat.



= kJ

Entropy changes for ideal gas

For ideal gases du = cvdT and pv = RT

Or p/T = R/v

Substituting these relations in eq (3) we get



= +

Integrating for a process 1 2 assuming constant specific heats

= + kJ/kg


= + kJ

Now dh = cpdT and and v/T = R/p

Substituting the above relations in eq (4) we get



=

Integrating for a process 1 2 assuming constant specific heats

= kJ/kg


= kJ

Statistical Interpretation of Entropy

Even though a system is in macroscopic equilibrium, microscopically the particles making up the
matter are in continuous motion. For any macroscopic equilibrium state of a system there will be a
large number of possible microscopic states. The total number of possible microscopic states available
to a system is called the thermodynamic probability, . The entropy of a system is related to by
Boltzmann relation

S = k ln

Where k is the Boltzmann constant k = 1.3806 x 10-23 J/K

k = Universal gas constant / Avogadro number

Any process that increases the number of possible microscopic states of a system increases its
entropy. As the number of microscopic states increases the randomness or the disorder of the system
increases. Entropy is therefore a measure of randomness or disorder of the system.

Third Law of Thermodynamics

The molecules of a substance in solid phase continually oscillate, creating an uncertainty about their
position. These oscillations fade as the temperature is decreased, and the molecules become
motionless at absolute zero. This represents a state of ultimate molecular order (and minimum
energy).
Therefore, the entropy of a pure crystalline substance at absolute zero temperature is zero since there
is no uncertainty about the state of the molecules at that instant. This statement is known as Nernst-
Simon statement of the third law of thermodynamics.

The third law of thermodynamics provides an absolute reference point for the determination of
entropy.

Fowler-Guggenheim statement of Third Law

It is impossible by any procedure, no matter how idealized, to reduce any condensed system to the
absolute zero of temperature in a finite number of operations.

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