In a heat engine, the temperature difference between

the hot region and the cold region is the measure of the
available energy.
However, the second law states that, in an isolated
system heat must flow from a hot region to a cold.
With time, therefore, this temperature difference must
decrease, for as the heat flows in the only direction it can
flow, the hot region cools down and the cold region
warms up.
Consequently, the available energy decreases with
time. Since the total energy remains constant, the
unavailable energy must increase as the available
energy decreases.
If an ideal frictionless reversible engine removes
Q
h
from some substance at T
h
, does some work,
and delivers Q
c
to some other substance at T
c
, then
Q
h
/Q
c
= T
h
/ T
c
or
Q
h
/ T
h
= Q
c
/ T
c
.
Clausius used the last expression to introduce
entropy, S.
Entropy
Definition: Consider any infinitesimal process in
which a system changes from one equilibrium state
to another. If dQ
r
is the amount of energy transferred
by heat when the system follows the reversible path
between the states, then the change in entropy dS is
equal to this amount of energy for the reversible
process divided by the absolute temperature of the
system, T:
dS = dQ
r
/T
The temperature is assumed constant because the
process is infinitesimal.
Entropy has units of Joules per Kelvin [J/K]
Entropy
Calculating entropy always use temperature in
Kelvin!
Consider a system in two different conditions, for
example 1 kg of ice at 0
o
C, which melts and turns into
1 kg of water at 0
o
C. We associate the entropy with
each condition.
The entropy of any substance is a function of the
condition of the substance.
For an ideal gas it is a function of its temperature and
volume, and for a solid and liquid it is a function of its
temperature and internal structure.
Entropy
The entropy is independent of the past history of the
substance. The entropy of the 1 kg of water at 0
o
C is the
same if we obtained the water from ice, or if we cooled the
water from room temperature down to 0
o
C.
Entropy is a state function (as temperature and internal
energy) because the change in entropy does not depend on
the path followed.
Sign:
When the energy is absorbed by the system, change in the
heat is positive and the entropy of the system increases.
When energy is expelled by the system, dQr is negative, and
the entropy of the system decreases.
Entropy
To calculate the change in entropy for a
finite process we need to integrate the energy
transferred by heat divided by the temperature
(which is not constant) along a reversible
path:
S =

=
f
i
f
i
T
dQr
dS
In Carno-engine, the entropy of the substance at T
h
decreases by Q
h
/ T
h
and the entropy of the
substance at T
c
increases by the same amount.
There is no net change in entropy, if we consider
the entire system.
But a real engine always delivers more heat at T
c
than a reversible engine. For a real engine Q
c
/ T
c
is always greater than Q
h
/ T
h
.
The entropy of the substance at T
h
decreases, but
the entropy of the substance at T
c
increases by a
larger amount. The entropy of the whole system
increases.
The total entropy of an isolated system is always
increasing is another way of stating the second law
of thermodynamics.
A closed system is a system that does not interact in
any way with its surroundings. In practice there are
really no closed isolated systems except, perhaps,
the universe as a whole.
Therefore we state the second law in the following
way: The total entropy of the universe is always
increasing.
Entropy
Entropy in thermal processes measures the extent to which
energy of a system is available for conversion to work.
If a system undergoing an infinitesimal reversible change takes
in a quantity of heat dQ at absolute temperature T, its entropy is
increased by:
dS = dQ
r
/T
The area under the absolute temperature-entropy graph for a
reversible process represents the heat transferred in the process.
S
T
Q
For an adiabatic process, there is no heat transfer and the
temperature-entropy graph is a straight line, the entropy remaining
constant through the process.
The first law of thermodynamics says that the total quantity of energy in
the universe remains constant. This is the principle of the conservation of
energy.
The second law of thermodynamics states that the quality of this energy
is degraded irreversibly. This is the principle of the degradation of
energy.
The first principle establishes the equivalence of the different forms of
energy (radiant, chemical, physical, electrical, and thermal), the possibility
of transformation from one form to another and the laws that govern these
transformations.
Physical, chemical, and electrical energy can be completely changed into
heat. But the reverse (heat into physical energy, for example) cannot be
fully accomplished without outside help or without an inevitable loss of
energy in the form of irretrievable heat.
This does not mean that the energy is destroyed; it means that it
becomes unavailable for producing work.
More About Change in Entropy
dQ
r
is measured along a reversible path,
even if the system may have followed an
irreversible path
The meaningful quantity is the change in
entropy and not the entropy itself
For a finite process,
Change in Entropy
The change in entropy of a system
going from one state to another has the
same value for all paths connecting the
two states
The finite change in entropy depends only
on the properties of the initial and final
equilibrium states
S for a Reversible Cycle
S = 0 for any reversible cycle
In general,
This integral symbol indicates the integral is
over a closed path
S for a Quasi-Static, Reversible Process
Assume an ideal gas undergoes a quasi-
static, reversible process
Its initial state has T
i
and V
i
Its final state has T
f
and V
f
The change in entropy is
This demonstrates that S depends on only
the initial and final states and not the path
between the states
Entropy and Heat
The change in entropy depends only on the
endpoints and is independent of the path
followed
The entropy change for an irreversible
process can be determined by calculating
the change in entropy for a reversible
process that connects the same initial and
final points
Entropy Changes in Irreversible Processes
To calculate the change in entropy in a real
system, remember that entropy depends
only on the state of the system
Do not use Q, the actual energy transfer in
the process
Distinguish this from Q
r
, the amount of energy
that would have been transferred by heat along a
reversible path
Q
r
is the correct value to use for S
In general, the total entropy and therefore
the total disorder always increases in an
irreversible process
The total entropy of an isolated system
undergoes a change that cannot decrease
This is another statement of the second law of
thermodynamics
Entropy Changes in Irreversible Processes
If the process is irreversible, then the total
entropy of an isolated system always
increases
In a reversible process, the total entropy of an
isolated system remains constant
The change in entropy of the Universe
must be greater than zero for an
irreversible process and equal to zero for a
reversible process
Entropy Changes in Irreversible Processes
Heat Death of the Universe
Ultimately, the entropy of the Universe should
reach a maximum value
At this value, the Universe will be in a state of
uniform temperature and density
All physical, chemical, and biological processes
will cease
The state of perfect disorder implies that no energy is
available for doing work
This state is called the heat death of the Universe
S in Thermal Conduction
The cold reservoir absorbs Q and its entropy
increases by Q/T
c
At the same time, the hot reservoir loses Q and
its entropy decreases by -Q/T
h
Since T
h
> T
c
, the increase in entropy in the cold
reservoir is greater than the decrease in entropy
in the hot reservoir
Therefore, S
U
> 0
For the system and the Universe
Adiabatic Free Expansion
This is an example of adiabatic
free expansion
The process is adiabatic because
it takes place in an insulated
container
Because the gas expands into a
vacuum, it does not apply a force
on a piston and W = 0
Since Q = 0 and W = 0, E
int
= 0
and the initial and final states are
the same
No change in temperature is
expected
S in a Free Expansion
Consider an adiabatic free expansion
Q = 0 but cannot be used since that is for
an irreversible process
S in Free Expansion
For an isothermal process, this becomes
?S = nRln(V
f
/V
i
)
Since V
f
> V
i
, S is positive
This indicates that both the entropy and
the disorder of the gas increase as a result
of the irreversible adiabatic expansion
S in Calorimetric Processes
The process is irreversible because the system
goes through a series of nonequilibrium states
Assuming the specific heats remain constant
and no mixing takes place:
If mixing takes place, this result applies only to
identical substances
S will be positive and the entropy of the Universe
increases