Entropy Change

P M V Subbarao
Professor
Mechanical Engineering Department

A Single Reason for Every Thing

That Happens!!!

The Thermodynamics of Temperature Creation

The Gibbsian equation,defines the change in specific
entropy of any substance during any reversible process.
Tds du pdv dh vdp
Consider a control mass
executing a constant
volume process:

Tds du pdv
u
T
s

v constant

The relative change in internal energy of a control mass w.r.t.

change in entropy at constant volume is called as absolute
temperature.

The Thermodynamics of Temperature Creation

Consider a control volume executing a reversible constant
pressure process:

Tds dh vdp
h
T
s

p constant

The relative change in enthalpy of a control volume w.r.t.

change in entropy at constant pressure is called as absolute
temperature.

Entropy change of an ideal gas

From the Gibbsian equations, the change of entropy of a
substance can be expressed as
du P
dh v
ds
dv or ds
dP
T T
T T
For an ideal gas, u=u(T) and h=h(T),
du=cv(T)dT and dh=cp(T)dT and Pv=RT

C p T dT v
cv T dT P
ds
dv or ds
dP
T
T
T
T
By Integration, the change in the entropy is

v2
dT

s2 s1 cv T
R ln
T
v1
1
2

or

p2
dT

s2 s1 c p T
R ln
T
p1
1
2

Ideal Gas with constant specific heats

When specific heats are constant (calorically perfect gas),
the integration can be simplified:

T2
v2
R ln

s2 s1 cv ln
T1
v1
T2
p2
R ln

s2 s1 c p ln
T1
p1
If a process is isentropic (that is adiabatic and reversible), ds=0,
s1=s2,

Isentropic Process with idea gas

T2
v2
R ln
0
cv ln
T1
v1

T2
p2
R ln
0
c p ln
T1
p1

T2
v2
R ln

cv ln
T1
v1

T2
p2
R ln

c p ln
T1
p1

T2
v2
cv c p ln

cv ln
T1
v1

T2
p2
c p cv ln

c p ln
T1
p1

c p v2
T2
1 ln

ln
cv v1
T1

p2
T2
c
v
1 ln

c p ln

c p p1
T1

T2
v2
1 ln

ln
T1
v1

T2
1 p2
1 ln

ln
p1
T1

 T2 v2

T1 v1
v2

v1

p2

p1

v2 p 2

v1 p1

T2 p2

T1 p1

v2 p2

v1 p1

p2 v2

p1 v1
p2 v1

p1 v2

p2v2 p1v1

Isentropic Process by an idea gas with constant

propeties
T2 v2

T1 v1
T

v

C1

T2 p2

T1 p1

or

p

T

C2

p2 v1

p1 v2

or

pv C3

Are the reversible Process practicable?

100% perfection is possible but may not ne practicable..!?!!?!

Practical Processes are influenced by Irreversibilities

Fluid friction
Solid friction
Electrical resistance
Thermo-chemical Reactions (Combustion)
Unrestrained motion
Heat Transfer with a finite temperature difference

Solid Friction is an Irreversibility

Q
PE KE

Solid Friction is an Irreversibility

Q
PE KE

Solid Friction is an Irreversibility

PE KE
Q

Solid Friction is an Irreversibility

Q

THIS IS NOT POSSIBLE.

Reverse

Solid Friction is an Irreversibility

1

Irreversible and Reversible engines

HTR
QHE
HEI
WnetI

QHER
WnetR

EI
QLE
LEI

ER
QLER

LTR

Assume that an irreversible

Engine is more efficient than
the reversible engine.

irr rev
Wnet , I
QHEI

Wnet , R
QHER

Wnet,I Wnet,R
>
QHEI QHER
For same Wnet,

QHEI < QHER

Implies that, |QLEI | < |QLER|

But a reversible engine can be completely reversed and it will
work as a heat pump.

For same |Wnet |,

rev

rev

irr

QHEI QHPR
rev

Let us construct a compound machine using an irreversible engine

and reversed reversible engine (reversible Heat Pump).

HTR (Sink)
|QHPR | - QHEI
QHEI < |QHPR |
QHPR

QHEI
WnetR

EI

R
QLPR

QLE
|QLEI| < QLPR

QLPR - |QLEI |
LTR (Source)

Irreversible Machines
The efficiency of an irreversible heat engine will always
less than the efficiency of a reversible engine working
between the same reservoirs.
The COP of an irreversible heat pump will always less
than the COP of a reversible heat pump working between
the same reservoirs.

Further Discussions
Isotop
irrrev

e
Half-Life
Decay
He-3 Stable
N/A
irrrev but, 1/revrev
Stable
N/A
He-4 0.5 x 10-21 sec - 1 x 10-21 sec p or n
irrrev1(Mathematically
He-5
x 10-21 sec possible but thermodynamically
n
impossible).
0.8 sec
He-6 5 x 10-23 sec - 5 x 10-21 sec
n
Similarly,3irrx
1/irr-
rev -21 sec
He-7
10rev-22sec
4 x 10
n
0.1 sec
He-8
x 10-21 secpossible
- 1 x 10
sec
n/
irrrev0.5
(Mathematically
but-21thermodynamically
He-9
unknown
unknown
impossible).

Increase of Entropy Principle

For a general Process
Define entropy generation Sgen as,

Increase of Entropy
Principle
Entropy
change

Entropy
Transfer
(due to heat
transfer)

Entropy Generation

The principle states that for an isolated Or a closed adiabatic Or

System + Surroundings;
A process can only take place such that Sgen 0 where Sgen = 0 for a
reversible process only and Sgen can never be less than zero.

Implications of Increase of Entropy Principle

Entropy, unlike energy, is non-conservative since it is always
increasing.
The entropy of the universe is continuously increasing, in
other words, it is becoming disorganized and is approaching
chaotic.
The entropy generation is due to the presence of
irreversibilities.
Therefore, the higher irreversibilities lead to the higher the
entropy generation and the lower the efficiency of a device.
The above is Engineering statement of the second law

Second Law & Entropy Balance

Increase of Entropy Principle is another way of stating the
Second Law of Thermodynamics:
Second Law : Entropy can be created but NOT destroyed
In contrast, the first law states: Energy is always
conserved.
Note that this does not mean that the entropy of a system
cannot be reduced, it can.
However, total entropy of a system + surroundings cannot
be reduced.

Entropy of Universe
A quantity of heat Q is spontaneously transferred from the
surroundings at temperature T0 to the control mass at temperature T.
Let the work done during this process be W.
For this process by control mass and write

For the surroundings at T0, Q is negative,

and we assume a reversible heat extraction
so

Net Change in Entropy of Universe

The total net change of entropy is therefore

Since T0 > T, the quantity [(1/T) - (1/T0)] is positive, and

we conclude that

If T > T0, the heat transfer is from the control mass to the
surroundings

It should be noted that the right-hand side of above equation

represents an external entropy generation due to heat transfer
through a finite temperature difference.

The Third Law of Thermodynamics

The entropy change of a system during a

reversible isothermal process tends towards
zero when the thermodynamic temperature
of the system tends towards zero.
In the neighbourhood of absolute zero, all
reactions in a liquid or solid in internal
equilibrium take place with no change in
entropy.
[Nernst 'principle'].

Plancks statement of the 3rd law

In 1911, Planck one step further and made the hypothesis
that not only does the entropy difference vanish as T 0,
but that:
Plancks statement of the Third Law: The entropy of every
solid or liquid substance in internal equilibrium at
absolute zero is itself zero.
Planck is just saying:

lim S 0
T 0

Engineering Relations from Second Law

Entropy as A Rate Equation

The second law of thermodynamics was used to write the
balance of entropy for a infinitesimal variation for a finite
change.
Here the equation is needed in a rate form so that a given
process can be tracked in time.
Take the incremental change and divide by t.
We get

 For a given control mass we may have more than one source of
heat transfer, each at a certain surface temperature (semidistributed situation).

The rate of entropy change is due to the flux of entropy into

the control mass from heat transfer and an increase due to
irreversible processes inside the control mass.

The Second Law Of Thermodynamics

For A Control Volume
The rate of change of property B of the system
.
dBCM dBCV

B out B in
dt
dt
Let B = Entropy of the system, S = ms.
dS CM dSCV
s out m
s in

m
dt
dt
dSCM
Q
S gen
dt
T

Entropy Rate Equation for CV

Rate of change in entropy of a CV = Entropy in flow rate Entropy

out flow rate + the flux of entropy into the control mass from heat
transfer + Rate of Entropy generation

The Steady State Steady Flow Process

For the steady-state process, which has been defined before,
we conclude that there is no change with time of the property
(entropy) per unit mass at any point within the control volume.
That is,

so that, for the steady-state process,

 If in a steady-state process there is only one area over

which mass enters the control volume at a uniform rate and
only one area over which mass leaves the control volume
at a uniform rate,
we can write

and dividing the mass flow rate out gives

Since sgen is always greater than or equal to zero, for an adiabatic

process it follows that

where the equality holds for a reversible adiabatic process.

Geometry of Turbine Blades for High Efficiency

Transient Process
For the transient process, the second law for a control
volume, it can be written in the following form:

If this is integrated over the time interval t, we have

Therefore, for this period of time t, we can write the second law
for the transient process as

Since in this process the temperature is uniform throughout

the control volume at any instant of time, the integral on the
right reduces to

and therefore the second law for the transient process can be
written

Mechanical Engineering Inventions

Carnot Cycle
Lenoir Cycle
Otto Cycle
Stirling Cycle
Atkinson Cycle
Diesel Cycle
Brayton cycle
Rankine Cycle
Vapour Compression Refrigeration Cycle
Vapour Absorption Refrigeration Cycle