1

Lec 18: Isentropic processes,

TdS relations, entropy changes
2
For next time:
Read: 7-2 to 7-9
Group project subject selection due on
November 3, 2003

Outline:
Entropy generation and irreversible processes
Entropy as a property
Entropy changes for different substances

Important points:
Entropy is a property of a system it is not
conserved and is generated by irreversible
processes
Know how to identify an isentropic processes
Know how to use the tables to find values for
entropy
3
Recall we had entropy




}
|
.
|

\
|
o
2
1
rev int
T
q
R lb
Btu
or
K kg
kJ
m

s
2
- s
1
=
Units
are
4
Lets look at a simple
irreversible cycle on a p-v
diagram with two processes
P
u
1
2
.
.
A
B
Let A be
irreversible and B
be reversible
5
Irreversible cycle
0 )
T
Q
AB
s
o
}
By Clausius Inequality
Evaluate cyclic integral
0
T
Q
T
Q
T
Q
2
1
B
2
1
A cycle
s
|
.
|
o

|
.
|
o
=
|
.
|
o
} } }
(non-rev) (rev)
6
Irreversible cycle
For the reversible process, B, dS=oQ/dT,
thus:
0 dS
T
Q
T
Q
2
1
2
1
A cycle
s
|
.
|
o
=
|
.
|
o
} } }
Rearranging and integrating dS:
}
|
.
|
o
> A
2
1
A
T
Q
S
7
Second Law of Thermodynamics
Entropy is a non-conserved property!
}
|
.
|
o
> = A
2
1
A
1 2
T
Q
S S S
This can be viewed as a mathematical
statement of the second law (for a
closed system).
8
We can write entropy change as an
equality by adding a new term:
gen
2
1
A
1 2
S
T
Q
S S +
|
.
|
o
=
}
entropy
change
entropy
transfer
due to
heat
transfer
entropy
production
or
generation
9
Entropy generation
S
gen
> 0 is an actual irreversible process.
S
gen
= 0 is a reversible process.
S
gen
< 0 is an impossible process.
10
TEAMPLAY
Consider the equation



You have probably heard, Entropy always
increases.
Could it ever decrease? What are the
conditions under which this could happen
(if it can)?

gen
2
1
A
1 2
S
T
Q
S S +
|
.
|
o
=
}
11
Entropy transfer and production
What if heat were transferred from the
system?
The entropy can actually decrease if
gen
2
1
A
S
T
Q
>
|
.
|
o
}
and heat is being transferred away
from the system so that Q is negative.
12
Entropy Production
S
gen
quantifies irreversibilities. The
larger the irreversibilities, the greater
the value of the entropy production,
S
gen
.
A reversible process will have no entropy
production.
13
Entropy transfer and production

S
2
S
1

> 0, Q could be + or ; if ,
because S
gen
is always positive.
< 0, if Q is negative and

= 0 if Q = 0 and S
gen
= 0.

= 0 if Q is negative and
gen
2
1
A
S
T
Q
>
|
.
|
o
}
gen
2
1
A
S
T
Q
<
|
.
|
o
}
gen
2
1
A
S
T
Q
=
|
.
|
o
}
14
Isentropic processes
Note that a reversible (S
gen
= 0),
adiabatic (Q = 0) process is always
isentropic (S
1
= S
2
)

But, if the process is merely isentropic
with S
1
= S
2
, it may not be a reversible
adiabatic process.

For example, if Q < 0 and

gen
2
1
A
S
T
Q
=
|
.
|
o
}
15
Entropy generation
Consider



What if we draw our system boundaries
so large that we encompass all heat
transfer interactions? We would
thereby isolate the system.
gen
2
1
A
1 2
S
T
Q
S S +
|
.
|
o
=
}
16
Entropy changes of isolated systems
And then


gen
2
1
A
1 2
S
T
Q
S S +
|
.
|
o
=
}
0
gen 1 2
S S S =
But S
gen
>0. So, the entropy of an
isolated system always increases. (This
is the source of the statement, The world
is running down.)
17
Entropy
) s s ( x s s
f g f
+ =
) T ( s ) p , T ( s
f
~
It is tabulated just like u, v, and h.
Also,
And, for compressed or subcooled liquids,
18

The entropy of a pure substance is determined from the tables, just as for
any other property
19
Ts Diagram for Water
20
TEAMPLAY
Use the tables in your book
Find the entropy of water at 50 kPa and
500 C. Specify the units.
Find the entropy of water at 100 C and
a quality of 50%. Specify the units.
Find the entropy of water at 1 MPa and
120 C. Specify the units.

21
Ts diagrams
}
= pdV w
Work was the area under the curve.
Recall that the P-v diagram was very
important in first law analysis, and that
22
For a Ts diagram

rev int
T
Q
dS
|
.
|

\
|
o
=
TdS Q
rev int
=
}
=
2
1
rev int
TdS Q
Rearrange:
Integrate:
If the internally reversible process also is
isothermal at some temperature T
o
:
S T dS T Q
o
2
1
o rev int
A = =
}
23

On a T-S diagram, the area under the process curve represents the
heat transfer for internally reversible processes
d
24
Entropy change of a thermal
reservoir
For a thermal reservoir, heat transfer occurs
at constant temperaturethe reservoir
doesnt change temperature as heat is
removed or added:
}
= A
T
Q
S
o
Since T=constant:
T
Q
S = A
Applies ONLY to
thermal
reservoirs!!!!
25
The Tds Equations
26
Derivation of Tds equations:
dQ dW = dU
For a simple closed
system:
dW = PdV
The work is given by:
dQ = dU + PdV
Substituting gives:
27
More derivation.
For a reversible process:
TdS = dQ
Make the substitution for oQ in the energy
equation:
PdV + dU = TdS
Or on a per unit mass basis:
Pdv + du = Tds
28
Entropy is a property. The Tds expression
that we just derived expresses entropy in
terms of other properties. The properties
are independent of path.We can use the
Tds equation we just derived to calculate
the entropy change between any two
states:
Tds = du +Pdv
Tds = dh - vdP
Starting with enthalpy, it is possible to
develop a second Tds equation:
Tds Equations
29
Lets look at the entropy change
for an incompressible
substance:
dT
T
) T ( c
ds =
We start with the first Tds equation:
Tds = c
v
(T)dT + Pdv
For incompressible substances, v ~ const, so
dv = 0.
We also know that c
v
(T) = c(T), so we can
write:
30
Entropy change of an
incompressible substance
dT
T
) T ( c
s s
2
1
T
T
1 2
}
=
1
2
1 2
T
T
ln c s s =
Integrating
If the specific heat does not vary with
temperature:
31
TEAMPLAY
Work Problem 7-48
32
Entropy change for an ideal gas
dT c dh
p
= And
dp
p
RT
dT c Tds
p
=
Tds = dh - vdp
Start with 2nd Tds equation
Remember dh and v for an ideal gas?
v=RT/p
Substituting:
33
Change in entropy for an ideal gas
p
dp
R
T
dT
c ds
p
=
Dividing through by T,
Dont forget, c
p
=c
p
(T)..a function of
temperature! Integrating yields
1
2
T
T
p 1 2
p
p
ln R
T
dT
) T ( c s s
2
1
=
}
34
Entropy change of an ideal gas
for constant specific heats:
approximation
Now, if the temperature range is so
limited that c
p
~ constant (and c
v
~
constant),

1
2
p p
T
T
ln c
T
dT
c =
}
1
2
1
2
p 1 2
p
p
ln R
T
T
ln c s s =
35
Entropy change of an ideal gas
for constant specific heats:
approximation
Similarly it can be shown from
Tds = du + pdv

that
1
2
1
2
v 1 2
v
v
ln R
T
T
ln c s s + =
36
TEAMPLAY
Work Problem 7-62
37
Entropy change of an ideal gas
for variable specific heats: exact
analysis
1
2
T
T
p 1 2
p
p
ln R
T
dT
) T ( c s s
2
1
=
}
}
2
1
T
T
p
T
dT
c
Integrating..
To evaluate entropy change, well
have to evaluate the integral:
38
} } }
= =
=
1 2 2
1
T
0 T
p
T
0 T
p
T
T
p
T
dT
c
T
dT
c
T
dT
c
) T ( s ) T ( s
1
o
2
o
=
And s
o
(T), the reference entropy, is
tabulated in the ideal gas tables for a
reference temperature of T = 0 and p = 1
atm.
Entropy change of an ideal gas
for variable specific heats: exact
analysis
Evaluation of the integral
39
Entropy change of an ideal gas for
variable specific heats: exact
analysis
Only is tabulated. The
is not.

So,
dT c
p
}
dT c
v
}
1
2
1
o
2
o
1 2
p
p
ln R ) T ( s ) T ( s s s =
40
Entropy change of an ideal gas
Note that the entropy change of an ideal
gas, unlike h and u, is a function of two
variables.
Only the reference entropy, s
o
, is a
function of T alone.
41
Sample Problem
A rigid tank contains 1 lb of carbon monoxide
at 1 atm and 90F. Heat is added until the
pressure reaches 1.5 atm. Compute:

(a) The heat transfer in Btu.

(b) The change in entropy in Btu/R.
42
Draw diagram:
State 1:
P = 1atm
T = 90
o
F
CO:
m= 1 lbm
State 2:
P = 1.5 atm
Rigid Tank => volume is
constant
Heat Transfer
43
Assumptions
Work is zero - rigid tank
kinetic energy changes zero
potential energy changes zero
CO is ideal gas
CO in tank is system
Constant specific heats
44
Apply assumptions to conservation
of energy equation
PE + KE + U W Q A A A =
( )
1 2 v
T T mc = Q
For constant specific heats, we
get:
0 0 0
Need T
2
> How do we get it?
45
Apply ideal gas EOS:
2
1
2 2
1 1
mRT
mRT
V P
V P
=
Cancel common
terms...
Solve for
T
2
:
( ) R 825 R 460 90
1.0
1.5
T
P
P
T
1
1
2
2
= +
|
.
|

\
|
=
|
|
.
|

\
|
=
46
Solve for heat transfer
( )R 550 825
R lb
Btu
18 . 0 ) lb 1 ( Q
m
m

|
|
.
|

\
|
=
Btu 5 . 49 Q=
Now, lets get entropy change...
47
For constant specific heats:
|
|
.
|

\
|
+ =
1
2
1
2
v 1 2
v
v
Rln
T
T
ln c m S S
Since v
2
= v
1

0
1
2
v 1 2
T
T
ln c S S =
|
|
.
|

\
|
|
|
.
|

\
|
=
R 550
R 825
ln
R lb
Btu
18 . 0 ) lb 1 ( S S
m
m 1 2
Btu/R 073 . 0 S S
1 2
=