Entropy

Entropy is appreciated through the microscopic approach where thermodynamics analysis is used
to account for energy quantities.
This is in contrast to the behavior of a system when investigated from the macroscopic or
classical approach where focus is on measurable gross quantities which can be perceived by our
senses like pressure, temperature, volume.
Microscopic (statistical) approach (Luti p23)
Consider a cube of 25mm sides containing monoatomic (molecules consist of single atoms e.g
helium, Xenon) gas at atmospheric pressure and temperature. The volume contains
approximately 1020 atoms.
To describe the position of each atom, we need to specify three coordinates; to describe the
velocity of each atom, we need to specify three velocity components.
This implies, to completely describe the behavior of this system from microscopic point of view
we need at least 6 x 1020 equations.
Using results from quantum mechanics and laws of probability applied to the large number of
particles, it is possible to show that the average behavior of these small particles exhibit itself as
the average or macroscopic state variables of classical thermodynamics. And all properties of
classical thermodynamics can be derived from statistical thermodynamics. Quantum mechanics
deals with mathematical description of the motion and interaction of sub atomic particles and is a
concept of quantization of energy, wave particle density, uncertainty principle.
The major drawback in using statistical thermodynamics is in the mathematics involved.
Entropy can be viewed as a measure of molecular disorder or molecular randomness. As a
system becomes more disordered, the positions of the molecules become less predictable and the
entropy increases.
In the solid phase, the molecules of a substance continually oscillate about their equilibrium
positions, they cannot move relative to each other, and their position at any instance can be
predicted with good certainty. And this results in lowest entropy state of a substance.
In the gas phase however, the molecules move about at random, collide with each other and
choose direction making it extremely difficult to predict accurately the microscopic state of the
system at any instant. This molecule chaos is associated with a high value of entropy.
Entropy is a measure of molecular disorder, and molecular disorder of an isolated system
increases any time it undergoes a process.
Molecules in a container in the gas phase possess a considerable amount of kinetic energy. But,
such kinetic energy will not rotate a paddle wheel and produce work, because the energy they
possess is disorganized.
Probably the number of molecules trying to rotate the wheel in one direction at any instant is
equal to the number of molecules trying to rotate it in the opposite direction, causing the wheel to
remain motionless.
Implying, we cannot extract any useful work directly from disorganized energy.
Consider operation of a paddle wheel in a container filled with gas.
The work of a paddle wheel will be converted to the internal energy of the gas, as evidenced by a
rise in gas temperature, creating a higher order of molecular chaos and disorder in the container.
The highly disorganized gas of energy cannot be converted back to the paddle wheel as
rotational kinetic energy. In the process the energy is degraded and the entropy increased.
The quantity of energy is always preserved during an actual process according to the first law of
thermodynamics. But the quality is bound to decrease according to the 2nd law of
thermodynamics, and the decrease in quality is always accompanied by an increase in entropy.
In all states the molecules of a substance continually oscillate, creating uncertainty about their
position. The oscillations fade as the temperature is decreased, and the molecules become
completely motionless at absolute zero.
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 is the 3 rd Law of
thermodynamics.
2nd Law was introduced and applied to cycles and cyclic devices. Applying the law to processes
requires the definition of the new property called entropy.
KJ
Entropy is an extensive property of a system, is designated S, and unit
Kg. K
δQ
By definition ds =
T

The change of entropy of a system during a process is given by:

2
∆ S=S 2−S1= ∫ δQ
1 T ( )
Note: It is the change in entropy that has been defined and not entropy itself. Like energy,
entropy is defined as a difference and is normally assigned zero value at an arbitrary state.
Although entropy change is defined only for a reversible process, since it’s a property, it can be
calculated for irreversible process.
For a process between states 1 and 2, the entropy change S2 - S1 is independent of the path. And it
is immaterial if the given process joining 1 and 2 is reversible or not.
We can always imagine a reversible process between the given states and calculate the change in
entropy which will also be the entropy change in the given irreversible process.
Proof that entropy is a property
d QR
Statement to prove: The integral of , when a system executes any reversible process
T
between fixed end states, is independent of the path of the process.

Let the system execute the reversible cyclic process from 1 along path A to 2 and back along
path C to 1.
2
d QR 1 d Q R
∫ T +∫ T =0 (10)
1 2

A C

Similarly, for the reversible process path 1B2C1 we have

2
d QR 1 d Q R
∫ T +∫ T =0 (11)
1 2
 B C

Subtracting equation (11) from (10) we obtain

2
d QR 2 d QR
∫ T =∫ T (12)
1 1

A B
2
d QR
Implying that ∫ has the same value for any reversible path between 1 and 2
1 T

Therefore, entropy is a property.

The Inequality of Clausius

Consider a reversible and irreversible engine operating between same two reservoirs. If the work
produced by the Carnot cycle is W rev and that produced by the irreversible cycle W irr
For the same amount of heat addition Q H we must have
W irr <W rev

Applying first law to the cycle.

 W =QH −QL (1)

And Q Lrev < Q Lirr

δQ Q H Q L
The cyclic integral can be expressed as ∫ = − (2)
T TH TL

And from the expression of efficiency

Q H −Q L QL
η= =1− (3)
QH QH

or
TL
η=1− (4)
TH

QL T L Q H Q L
Implying = ∨ = (5)
QH T H T H T L

Substitution of (5) into (2) yields

δT
∮ T
=0

Note: 2nd law leads to expression that involves inequalities e.g. efficiency of irreversible engine
is less than that of a reversible engine operating between same thermal reservoir.
-An irreversible refrigerator/heat pump has a lower Coefficient of performance (COP) than a
reversible one operating between same temperature limits.
The symbol ∮indicates the integration is performed over the entire cycle. Any heat transfer to
and from the system can be considered to consist of differential amounts of heat transfer and the
δQ
cyclic integral is the sum of all these differential amounts of heat transfer divide by the
T
absolute temperature at the boundary.
Another important inequality, which is also a consequence of the 2nd law, was stated by Clausius
as
δQ
∮ T
≤0

δQ
That is the cyclic of is always less than or equal to zero.
T
The inequality is valid for all cycles, reversible and irreversible and that when:
δQ
∮ T
=0 Cycle is reversible

δQ
∮ T
<0 Cycle is irreversible

δQ
∮ T
>0 Cycle is impossible

Entropy Change for an Irreversible Process

Consider a cycle composed of two reversible processes along path A and B. And that the return
process along path C is irreversible.
For the reversible cycle:
2 1

∫ δQ +∫
δQ
=0 (1)
1 T 2 T

A B

For a cycle involving the irreversible process the Clausius inequality demands that
 2 1

∫ δQ +∫
δQ
<0 (2)
1 T 2 T

A C

Subtracting (1) from (2)

1 1

∫ δQ
T
>∫
δQ
(3)
2 2 T

B C
δQ
But along reversible path B, =dS
T
Therefore, for any path
δQ δQ
∆ S ≥∫ or ds ≥ (4)
T T
The equality holds for reversible process and inequality for an irreversible process.
The relationship lead to important conclusions in thermodynamics.
Consider an infinitesimal heat transfer δQ to a system at absolute temperature T.
δQ
i. If the process is reversible, the differential change in entropy is
T
δQ
ii. If the process is irreversible, the change in entropy is greater than
T
This leads to the conclusion that the effect of irreversibility (e.g. friction) is to increase the
entropy of a system.
An isolated system exchanges no work or heat with its surroundings while entropy change is due
to irreversibility , whose effect is always an increase in entropy.
An isolated system may consist of any number of subsystems.
A system and its surroundings can constitute an isolated system an isolated system since both
can be enclosed by a sufficiently large arbitrary boundary across which there is no heat, work or
mass transfer.
The entropy change of this isolated system during a process is the sum of the entropy changes of
the system and its surroundings.
Since no actual process is truly reversible, we can conclude that some entropy is generated
during a process and therefore the entropy of the universe which can be considered to be an
isolated system is continuously increasing.
Some conclusion on Entropy
1) Processes can occur in a certain direction only not in any direction. A process must
proceed in the direction that complies with the increase of entropy principle ( Δ s ≥ 0 ¿ , a
process that violates this principle is impossible.
2) Entropy is a non-conserved property and that of the universe is continuously increasing.
3) The performance of engineering systems is degraded by the presence of irreversibility’s
and entropy generation is a measure of the magnitude of irreversibility’s present during
that process.
Entropy changes for perfect gas
By definition
dQ=mC p dT For non-flow constant pressure process
dQ=mC v dt For non-flow constant volume process

Using dQ=dU + dW (Non-flow energy equation)

For constant volume process

dw=0
Therefore dQ=dU
And for a perfect gas
dQ =M C V dT

Therefore
dQ =dU =CvdT
And on integration
U =CvT +C
But according to Joules law, internal energy varies linearly with temperature.
For a perfect gas: Assuming U =0 at T =0 , implies that C=0
Therefore, U =C v T
Non flow energy equation for reversible process
dQ=dU + pdV
And for perfect gas
dV
dQ=C v dT + RT
V
Dividing through by T
dQ dT dV
=C v +R
T T V
For adiabatic process dQ=0
dQ dT dV
i.e. =CV +R =0
T T V
For any other reversible process
dQ
dS=
T
Integrating gives
2
dQ
S2−S 1=∫
1 T

From dQ=Tds
For reversible process
 2
Q=∫ Tds
1

Which is analogues to
2
W =∫ pdV
1

Therefore, as there is a diagram on which areas represent work done in a reversible process there
is also a diagram on which area represent heat flow in a reversible process. The diagrams are the
PV and the TS diagrams.