Chapter 6: Using Entropy

Photo courtesy of U.S. Military Academy photo archives.

Combining the 1st and the 2nd Laws of Thermodynamics

Introducing Entropy

Up until now we have presented corollaries of the

second law for systems undergoing a cycle between
two thermal reservoirs.

Now, we are going to introduce a corollary of the

second law known as the Clausius inequality.

The Clausius inequality is applicable to any cycle

without regard for the bodies from which the
cycle receives energy (unlike previous corollaries).

1
 Introducing Entropy

The Clausius inequality provides the basis for

introducing two ideas that will become tools for
the analysis of both closed and open systems
from the point of view of the 2nd law of
thermodynamics.
The property entropy
Entropy balance

Clausius Inequality

The Clausius inequality states that for any thermodynamic

cycle
Q
T b 0
Where Q represents the heat transfer at a part of the
system boundary during a portion of the cycle
T is the absolute temperature at that part of the boundary
and b stands for boundary
The symbol indicates that the integral is to be performed
over all parts of the boundary and over the entire cycle

2
 Clausius Inequality

Consider the Reversible Inter. Cycle

QH QC
from Kelvin temp.
TH TC
we can rewrite this for the Inter. cycle
Q Q Reversible

Tres T b

Energy balance on the dotted system

dECycle Q WCycle

Using the definition for Q ' above

Q
WCycle Tres dECycle
T b

Clausius Inequality

For a Cycle we know that:

0
Q
WCycle Tres dECycle
T b

Then we end up with

Q
Wcycle Tres
T b

From the Kelvin-Planck Statement

Wcycle 0 (interaction w/ single reservoir)

Then, the Clausius inequality is born

Q
0
T b

3
 Clausius Inequality

As the Kelvin-Planck statement, the less

than sign is associated with irreversibilities
and the equal sign is associated with a
reversible system.

Q
T b 0

Clausius Inequality

For an internally reversible system

Q
0
T int
rev

A corollary to the definition of a property is that any

quantity whose change during a cycle is always zero is a
property of the system. Therefore, Q/T represents the
change in a thermodynamic property. In 1865 Clausius
named it entropy.

4
Relationship Between Cyclic Integrals and System Properties

Consider the volume occupied

by a gas in a piston-cylinder
device (shown in figure).

Since the initial volume and

final volume are the same, then
the net change in volume is
zero.

dV Vcycle 0

The same can be said for any

The net change of a property
property such as energy. during a cycle is always zero

Clausius Inequality

Hence, since the Clausius Inequality can be written as

Q
0
T int
rev
Then

Q
int property
T rev
Which is called entropy and is represented by the letter S

5
 Entropy Change
For a cycle it
For a finite, internally reversible path: has to be zero,
but not for a
process.

Q 2Q
dS S 2 S1
1 T int
T int
rev
rev

Differential form of the Definition of the change

change of entropy of entropy (the property)

Capital S
Units:
SI = kJ/K or kJ/kg-K (kJ/kmol-K)
English = Btu/R or Btu/lb-R (Btu/lbmol-R)
Small s

Finding Entropy Data

For Water and Refrigerants:

Motivation: Application of the 2nd Law of Thermodynamics frequently

requires finding specific entropy data.

Using Tables A-2 A-18

For example: P1 = 3 MPa Look for the specific entropy

T1 = 500 oC of water at the given state
s T , p s f T
Use Table A-4;

s1 = 7.2338 kJ/kg K
Saturation Data:

s (1 x) s f xsg s f x( sg s f )

Liquid Data: In the absence of tables, use the Compressed Liquid Rule

6
 Graphical Entropy Data

Temperature-Entropy Diagram Enthalpy-Entropy (Mollier) Diagram

T dS Equations

Consider a pure, simple compressible system undergoing

an internally reversible process. If KE = PE = 0, then the
energy balance can be expressed as follows:

Q intrev dU W intrev (1)

By definition of a simple compressible system, the

work is:
W int p dV
rev
(2)

By rearranging the differential form of entropy we get:

Q intrev T dS (3)

7
 T dS Equations
Inserting equations (2) and (3) into (1) we get the first
T dS equation.
T dS dU p dV (4)

The second T dS equation can be obtained from

equation (4) and the definition of enthalpy (H=U+pV).
The differential form of enthalpy is as follows.
dH dU d ( pV ) dU p dV V dp (5)

Putting (4) and (5) together, we get the second T dS

equation.
T dS dH V dp

T dS Equations

TdS dU PdV
Per Unit Mass:
Tds du Pdv

TdS dH VdP
Per Unit Mass: Tds dh vdP

8
 Example T dS Equation

Consider a change in phase form saturated liquid to saturated

vapor (at constant temperature and pressure of course). From
the second T dS equation we have,
0 (constant pressure)
T ds dh v dp
then we can rearrange the equation in the following form
dh
ds
T
Since the temperature is constant during the phase change, then
h hf
sg s f g (6)
T
This relationship shows how sg - sf is calculated for tabulation in property tables.

Example T dS Equation

Consider Refrigerant R-134a at 0C. From table A-10, hg-hf

= 197.21 kJ/kg. Using equation (6) we get:

197.21kJ/kg kJ
sg s f 0.722
273.15 K kg K

The actual tabulated values for the specific entropy are:

sg = 0.919 kJ/kg-K and sf = 0.197 kJ/kg-K

sg s f 0.919 0.1970 0.722 kJ/kg K

9
 Finding Entropy Data
For Ideal Gases:

Motivation: Application of the 2nd Law of Thermodynamics frequently

requires finding specific entropy data.

We start by rewriting the T dS equations in the following

fashion: du p
ds dv
T T
dh v
ds dp
T T

Since for an ideal gas du = cv(T) dT, dh = cp(T) dT and pv =

RT, then the T dS equations give.

dT dv dT dp
ds cv T R and ds c p T R (7)
T v T p

Finding Entropy Data

For Ideal Gases:

On integration, equation (7) gives:

T2 dT v (8)
s T2 , v2 s T1 , v1 cv T R ln 2
T1 T v1
T2 dT p (9)
s T2 , p2 s T1 , p1 c p T R ln 2
T1 T p1
To evaluate equations (8) and (9), we need to know how the
specific heats vary with temperature. Since these equations
require the integration of a function, then Eq. (8) and (9) are
more suitable for computer programming.

10
 Finding Entropy Data
For Ideal Gases:

For the purposes of this class, we prefer to work with tabulated values.
And, of course, there is a way to turn equations (8) and (9) user friendly
by using tables.

We start by setting a reference. Lets say the specific entropy is zero when
the temperature is 0 K (3rd law of thermo: entropy approaches 0 as
absolute temp. approaches 0 in perfect crystalline structures) and the
pressure is 1 atm. By using Eq. (9) to evaluate the entropy at a state where
temperature is T and pressure is 1 atm with respect to the reference, we
end up with the following expression.

T c p T
s T dT
0 T

Finding Entropy Data

For Ideal Gases:

where s(T) denotes the specific entropy at temperature T and

pressure of 1 atm. Since s depends only on temperature, it can
be tabulated versus temperature like u and h (see tables A-22
and A-23).

We can now use equation (9) with the tables by reformulating

the equation as follows:
P
s T2 , P2 s T1 , P1 s (T2 ) s (T1 ) R ln 2 For use with Table A-22
P1
P
s T2 , P2 s T1 , P1 s (T2 ) s (T1 ) R ln 2 For use with Table A-23
P1

Unlike u and h, entropy (s) DOES NOT depend solely on temperature for ideal gases

11
 Ideal Gases
with Constant Specific Heats

T P
s T2 , P2 s T1 , P1 C p ln 2 R ln 2
T1 P1

T v
s T2 , v2 s T1 , v1 Cv ln 2 R ln 2
T1 v1
Use Specific heat data in Tables A-20(E) and A-21(E)

12
 Ideal Gases
with Constant Specific Heats

For example, lets determine the change in specific entropy of

air as an ideal gas undergoing a process form T1 = 300K, p1 =
1bar to T2 = 400K, p2 = 5bar.

Because T is small, we can assume c p constant

evaluated at Tavg 350 K . c p 1.008 kJ kg K from Table A-20
T2 P
Using s c p ln R ln 2
T1 P1
kJ 400 K 8.314 kJ 5 bar
= 1.008 ln ln
kg K 300 K 28.97 kg K 1 bar
= 0.1719 kJ kg K

13
 Ideal Gases
with Constant Specific Heats

For example, lets determine the change in specific entropy of

air as an ideal gas undergoing a process form T1 = 300K, p1 =
1bar to T2 = 400K, p2 = 5bar.

Because T is small, we can assume c p constant

evaluated at Tavg 350 K . c p 1.008 kJ kg K from Table A-20
T2 P
Using s c p ln R ln 2
T1 P1
kJ 400 K 8.314 kJ 5 bar
= 1.008 ln ln
kg K 300 K 28.97 kg K 1 bar
= 0.1719 kJ kg K

Finding Entropy Data

For Incompressible Substances

For an incompressible substance, the change in specific

volume is approximately zero. Then,
0
c T dT pdv c T dT
ds
T T T
Incompressible substance model is generally used with liquids
and solids only, and assumes constant specific volume and
constant specific heat.

T2
s2 s1 c ln
T1
ClipArt courtesy of M.S. Office 2002

14
 Entropy

Q Q

T T 0
b b
cycle

Where cycle can be viewed as representing

the strength of the inequality.

cycle 0 no irreversibilities present within the system

cycle 0 irreversibilities present within the system
cycle 0 impossible

Unlike mass and energy, which are conserved in every

process, entropy in the presence of irreversibilities, is
always produced.

Entropy

Consider a cycle executed by a closed system,

which consists of two processes:
Process I (irreversibilities are present)
Process R (internally reversible)

Q
For this cycle we can rewrite T cycle as:
b

2 Q 1 Q
1 2
T b

T int
(1)
rev

Associated Associated
Process I Process R

15
 Entropy

We know, from a reversible process, that:

1 Q
2 S1 S 2
T int
rev

Therefore, we can rewrite equation (1) as follows.

2 Q
S1 S 2 (2)
1
T b

Finally, on rearranging equation (2), the closed system

entropy balance results.

Entropy Balance: Closed Systems

2
Q
S 2 S1
Units:
kJ/K
1 T b
Entropy Entropy Entropy
Change Transfer Production
Since measures the effect of irreversibilities present within
the system during a process, its value depends on the nature
of the process, and thus is NOT a property

Other common forms of the entropy balance:

dS Q Q Units:
j S 2 S1
Tb kW/K
dt j Tj

Rate basis Uniform Boundary Temperature

16
 Entropy Balance: Closed Systems

2
Q
S 2 S1
1 T b
It is important to remember the requirements that the second
law imposes on the equation above.

0 irreversibilites present within system

: 0 NO irreversibilities present
0 IMPOSIBLE

On the other hand:
0

S 2 S1 : 0 All permutations are possible
0

Example

Conocido: R-134a es
comprimido adiabatica-
mente en un sistema
cilindro-pistn desde
vapor saturado a 10F a
una presin final a 120
lbf/in2.

Buscar: Determinar el
trabajo mnimo terico de
entrada por unidad de
masa.

17
 Increase in Entropy Principle:
Closed Systems

Lets consider an enlarged system comprising a system and the

portion of the surroundings affected by the system as it undergoes
a process. Since all energy and mass transfer occurs within the
boundary, then:

E isol 0
Because no energy transfer
take place across its boundary.

Since energy its an extensive property, its value for the isolated
systems is the sum of its value for the system and surroundings.
ENERGY IS CONSERVED.

E system E surr 0

Increase in Entropy Principle:

Closed Systems

An entropy balance for the isolated

enlarged system yields:
0

2 Q
S isol isol
1
T b

S isol isol

18
 Increase in Entropy Principle:
Closed Systems

The summation of the entropy changes of

surroundings AND system must always
increase or remain the same

S system S surr total

total 0 ideal
total 0 actual
total 0 impossible

For any real process of an isolated

system, the entropy always increases

Example 6.5

Conocido: Una barra de metal,

inicialmente a 1900R, es removida
de un horno y sumergida en un
tanque cerrado el cual contiene
agua a 530R. Las propiedades de
las dos substancias son conocidas.
El tanque est bien aislado.

Buscar: Asumiendo calor

especifico constante, determina
La temperatura final de equilibrio, en
R
La cantidad de entropa producida, en
Btu/R

19
 Finding Entropy Data
Internally Reversible Processes

Internally reversible
processes are idealizations,
but are found in all Carnot
cycles.
Q
dS
T int
rev
2
Qint TdS
rev 1

For internally reversible

processes, the area under the
process curve represents the
process Heat Transfer.

Finding Entropy Data

Internally Reversible Processes

The figures show Carnot

cycles on the T-S
diagram.

The upper diagram

represents a power cycle

The lower diagram

represents a refrigeration
or heat pump cycle.

20
 Finding Entropy Data
Internally Reversible Processes

For a power cycle, QH = Q23 =

TH(S3-S2) and QC = Q41 = TC(S1-S4).
QH
Hence, Qcycle = QH + QC = (TH-
TC)*(S3-S2)

Since Qcycle = Wcycle for any cycle,

then
QC
Carnot
Wcycle T T S3 S2
H C
QH TH S3 S 2

Finally, T-s diagram Carnot power cycle

TC
Carnot max 1
TH

Problem 6.31

Known: The figure

provides the T-s diagram of
a Carnot heat pump cycle
for which the substance is
ammonia.

Find: For 50 cycles of

operation and 0.1 kg of
substance, determine
a) Net work input, kJ
b) Coefficient of performance

21
 Entropy Rate Balance:
Control Volumes

dScv Q
j mi si me se CV
dt j Tj i e

Rate of Rate of
Rates of entropy transfer
entropy entropy
change production

At Steady-State:

Qj
0 mi si me se CV
j Tj i e

Entropy Rate Balance:

Control Volumes

For one inlet and one exit system at steady state

1 Q
s2 s1 j CV

mi j T j mi
Special Cases:
Adiabatic Reversible & Adiabatic

CV s2 s1 isentropic
s2 s1
mi

22
 Example: Claim Verification

Conocido: Un inventor
reclama haber desarrollado
un aparato que operando en
S.S. produce corrientes de
aire fra y caliente de una sola
corriente a una temp.
intermedia sin transferencia
de calor trabajo.
Assume air as an ideal gas
with constant specific heat.
Buscar: Evaluar si este
aparato opera segn m3 0.6 m1
reclamado.

Vortex Tubes

The vortex tube, also known as the Ranque-Hilsch vortex tube, is a heat
pump with no moving parts. Pressurized gas is injected into a specially designed
chamber. The chamber's internal shape, combined with the pressure,
accelerates the gas to a high rate of rotation (over 1,000,000 rpm). The gas is
split into two streams, one giving kinetic energy to the other, and resulting in
separate flows of hot and cold gases.
Source: wikipedia.org

23
 Problem 101

Known: An inventor has

provided steady-state operating
data for a cogeneration system
that produces power and
increases the temp of air. The
system receives and discharges
heat at the rates and
temperatures described on the
figure.

Find: Assuming that kinetic

and potential energy effects are
negligible, determine if this
system can operate as
presented.

Isentropic Processes

Showing isentropic
processes is rapid
on T-s or h-s
diagrams. However,
tabular data may
still be used as well.
P
s2 P2 , T2 s1 P1 , T1 s2 T2 s1 T1 R ln 2
P1
Isentropic Processes with Ideal Gases
P
s 2 ( T 2 ) s1 ( T1 ) R ln 2
P1
P2 Pr 2 T Constant Specific Heats:

P1 Pr1 T k 1
For air only k 1
(Table A-22(E)) v2 vr 2 T T2 P2 k v k = cp/cv
1
: v1 vr1 T T1 P1 v2

24
25
 Isentropic Efficiencies

Comparing actual (adiabatic) and isentropic devices with

- same inlet states
- same exit pressure
Turbines

Wcv
1st Law:
h1 h2 2

m This helicopter gas turbine engine photo is courtesy of the

U.S. Military Academy.
Turbine
W
Isentropic Turbine Efficiency:
1

cv
2nd Law:
s2 s1 0 Wcv

m
m actual h1 h2 Actual Performance
T
s2 s1 real (irreversible) h1 h2 s Ideal Performance
W
cv
s2 s1 ideal (reversible) m
s

Isentropic Efficiencies
Comparing actual (adiabatic) and isentropic devices with
- same inlet states
- same exit pressure

Turbines

Wcv
1st Law:
h1 h2 2

m
Turbine
W

1 Isentropic Turbine Efficiency:

cv

2nd Law: s2 s1 0

Wcv

m m

actual h1 h2

T
Typical isentropic efficiencies for well
h1 h2 s
designed turbines vary from 70% to 90%. Wcv
m
s

26
 Isentropic Efficiency
Nozzles

V
1 V
Nozzle 2

V22 / 2
N 2
V2 s / 2
Typical isentropic efficiencies for
nozzles are around 95%. This implies
that well-designed nozzles are nearly
free of internal irreversibilities.
Clipart courtesy of M.S. Office 2002

Isentropic Efficiencies:
Compressors and Pumps

Compressors and Pumps:

Wcv
m
h h
C s 2 s 1
h2 h1
Wcv

m
actual

Pumps, assuming incompressible model:

v P2 P1 s
P Typical isentropic efficiencies for
compressors and pumps vary from
h2 h1 75% to 85%.

27
 Ejemplo: Eficiencia Isoentrpica

Conocido: Una turbina de

vapor de agua opera en S.S.
con condiciones de entrada
de P1=5bar, T1=320C. El
vapor sale de la turbina a
una presin de 1 bar.

Buscar: Asumiendo Q,
KE y PE = 0, determina
el trabajo desarrollado por la
turbina (kJ/kg) si la
eficiencia isoentrpica es
75%.

Ejemplo: Eficiencia Isoentrpica

Conocido: Vapor de agua

se expande en un inyector
en S.S. con estados de
entrada y salida
especificados. La
velocidad es conocida en
la entrada.

Buscar: Asumiendo Q y
PE = 0, determina la
eficiencia isoentrpica del
inyector.

28
 Heat Transfer and Work for
Internally Reversible Processes

Internally Reversible, Steady-State Flow:

2 2
Q cv Tds W cv vdP
1 m 1 (ke = pe = 0)
m int
rev
int
rev

Internally reversible, Steady-State, Incompressible fluid:

W cv v P2 P1
m

int
rev

Steady State, no significant work terms (nozzles and diffusers):

2
V22 V12
vdP g z2 z1 0
1
2
This equation, used commonly in fluid mechanics, is known as the Bernoulli equation

Compressor Work: Intercooling

Internally reversible, Steady-

State work:

W cv vdp
m
int
rev

29
 Polytropic Processes

PV n constant

Recall that for isentropic processes

k 1
k 1
T2 P2 k v
1
T1 P1 v2

By rearranging the equation above, we get:

k k
Pv
1 1 P2 v2 constant

Special Cases for n:

n=0: Isobaric
n=1: Isothermal
n=k: Isentropic
n=: Isometric (isochoric)

Work in Polytropic Processes

PV n constant

For Polytropic Processes

W cv n P2 v2 Pv
1 1
W cv Pv P2
1 1 ln
(n 1) (n=1)
m n 1 m P1
int
rev
rev
int

For Ideal Gases:

n 1 n
W cv nR T2 T1 (n 1) W cv nRT1 p2 1 (n 1)
m n 1 m n 1 p1
int
rev
int
rev

W cv RT ln P2 (ideal gas, n=1)
m P1
int
rev

30
Textbook Problem
Conocido: Aire como gas ideal entra a un
compresor operando en S.S. a 17C, 1 bar y sale a
una presin de 5 bar.

Buscar: Si KE y PE pueden ser ignorados y no

hay irreversibilidades internas, evala la potencia,
en kJ/kg, para los siguientes casos:
Compresin isotermal
Compresin polytropica (n=1.3)

Compresin adiabtica

31