4/11/2013

BITS Pilani
Pilani Campus

Lecture 26 What is entropy?

4/11/2013

Principle of entropy increase

Consider a closed system in adiabatic enclosure undergoing
an irreversible process a b.
b What can we say about Sb
Sa?
Return the system to state a by a reversible process, with
any heat exchange happening with a single reservoir at Tr.
Clearly Qba 0
For
F the
th cycle,
l Qba = Wba + Wba
Can Qba be positive? No, but why not?
Because Kelvin-Planck statement will be violated
Therefore Qba < 0, ie., Sa Sb < 0
ie.,
ie Sb > Sa. The entropy of a closed system in an adiabatic
enclosure cannot decrease. Isolated system a particular case
(S)isolated 0
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4/11/2013

Entropy creation and transfer

Let a closed system undergo an infinitesimal process
d i which
during
hi h there
th
is
i ah
heatt ttransfer
f Q with
ith a reservoir
i att
Tr.
dSsystem + dSreservoir 0.ButdSr =- Q/Tr
dSs + dSr = Sgen 0, defining the entropy generation
dSs = Q/Tr + Sgen
Entropy transfer accompanies heat transfer
Process

Entropy Entropy Entropy

change transfer creation

Work

Lost
work

Rln 2

R ln 2

RTln 2

Rln 2

R ln 2

Rln 2

0.5R

0.19R

0.5RT

?
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4/11/2013

Clausius inequality
From dSs = Q/Tr + Sgen, with Sgen 0
0, we have
dSs Q/Tr , the Clausius inequality (meaning?)
For a cycle Q/Tr 0

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4/11/2013

What is entropy?
Reversible work versus reversible heat transfer
Consider an ideal gas (non-interacting point particles)
What is the effect of a reversible adiabatic decrease in the
volume?
What is the effect of a reversible transfer of heat at constant
volume?
What happens in the course of the free expansion process
that we have discussed in some detail?
What is entropy?
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4/11/2013

Spontaneity and Equilibrium

Isolated system spontaneously evolves to states of greater
entropy
What therefore is the criterion that characterizes the
equilibrium state of an isolated system?
Maximum Entropy

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4/11/2013

Irreversibility and entropy

Due to nature of matter at microscopic level
Large scale natural processes eventually some kind of mixing
of particles or over available space
In some cases the mixing or sharing is of energy, as in the
equalization
li ti off th
the ttemperature
t
off bl
blocks
k
In friction, kinetic energy of body as a whole into random energy
of component molecules
Chemical reaction at equilibrium,
q
, the available energy
gy is
distributed over the available quantum states in the most random
possible manner
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4/11/2013

Entropy and Mixing - Spreading

Two distinct kinds
Spreading of particles over space
Spreading of available energy of system among available
particles and their states
p
The two effects may oppose one another under adiabatic
isolation, equilibrium determined by maximum in the overall
randomness
randomness or spreading configurational + thermal
Illustrate with discussion of diffusion

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4/11/2013

Natural processes and Microstates

Thermodynamic state or macrostate
Quantum state or microstate
A macrostate comprises an astronomical number of
microstates in a typical
yp
macroscopic
p system
y
Natural process is one in which there is an increase in ,
the number of microstates
Loss of detailed knowledge
knowledge, inability to predict which
microstate the system is in

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4/11/2013

Entropy and
Adiabatic mixing of A and B
Increase in , which in turn is a measure of the decrease
in information about the actual state
Increase in entropy
py S
= (U,V,N) and S = S(U,V,N), both are functions of
state. How are they related to one another?
S = k ln Boltzmann formula for entropy

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Entropy and
S = k ln . In previous example, assuming no energetic
distinctions, S = k ln(70)
S as a measure of thermodynamic probability, also
measured by
Mixed-up-ness, order and disorder case of adiabatic
change of super cooled liquid water to ice greater thermal
disorder, greater configurational order
Increase of S system spread over larger number of
possible quantum states loss of information
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Ideal monatomic gas

Non-interacting structure-less point particles
Translational states, given by particle in box model, very
closely spaced, virtually a continuum
Translational state energies
g
depend
p
on the size,, ie.,,
volume of the box work versus heat
Accessible states for a particle, z = (2mkT/h2)3/2V
For the gas of N particles
particles, Z = zN/N! Measures the number
of thermally accessible quantum states or microstates

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Ideal monatomic gas

S = Nk ln V + 3/2 Nk ln T + constant
If T1 = T2, S = Nk ln(V2/V1)
Comparing to the result we had earlier, for 1 mole, can find k.
Entropy
py increase due to more accessible levels at lower
energy
If V1 = V2, S = 3/2 Nk ln(T2/T1)
Entropy increase because levels at higher energy accessible
If S = 0, TV2/3 = constant
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