1

Second Law of Thermodynamics

Important definitions: reversible, irreversible, or impossible processes, heat
reservoirs, Clausiusstatement, Kelvin-Planck statement
Irreversible processes occur when some inefficiency (e.g., friction, pressure
gradients, temperature gradients) requires additional work to return a systemto
its starting state. These inefficiencies result in lost work and an increase in the
disorganization of energy in the universe (increase in entropy).
Reversible processes have no sources of lost work. Energy is moved fromone
place to another but no disorganization occurs (entropy remains unchanged).
No process is possible which reorganizes distribution of energy (entropy can not
decrease for the universe as a whole).
Reversible processes result in the maximumefficiency possible. Irreversible
processes will have lower efficiencies (i.e., less work output, larger heat rejection,
larger heat input, or larger work input).
For a reversible cycle:
(the temperature scale is defined this way)
As a result, maximumefficiencies for power and refrigeration cycles are:
100% efficiency cannot be achieved since T=0 K reservoirs dont exist
Temperature reservoir: a reversible body which accepts or provides heat but that
does not change temperature (atmosphere, ocean, lake, river, etc.)
H
L
H
L
T
T
Q
Q
=
q
m ax
= 1
T
T
L
H
L H
L
in out
in
cycle
in
rev refrig
T T
T
Q Q
Q
W
Q

= =
,
|
L H
H
in out
out
cycle
out
rev hp
T T
T
Q Q
Q
W
Q

= =
,

CARNOT CYCLE
CARNOT CYCLE =Ideal =Reversible
One idealized reversible cycle is the Carnot cycle which occurs
between a hot and a cold thermal reservoir at temperatures of TH
and TC respectively.
The Carnot Power Cycle: Four internally reversible processes
Process 1-2: Adiabatic compression from T1=TC to T2=TH.
Process 2-3: Isothermal expansion, heat transfer from nearly equal
temperature reservoir (TH)
Process 3-4: Adiabatic expansion to T4=TC.
Process 4-1: Isothermal compression, heat transfer from nearly
equal temperature reservoir
The Carnot Cycle
Since the Carnot cycle is reversible, the efficiency is maximized.
What do the T-v and p-v diagrams look like?
2
Examples
One-half kg of water executes a Carnot power cycle. During the
isothermal expansion, the water is heated until it is a saturated
vapor from an initial state where the pressure is 15 bar and the
quality is 25%. The vapor then expands adiabatically to a pressure
of 1 bar while doing 403.8 kJ /kg of work. (a) sketch the cycle on a
p-v diagram, (b) evaluate the heat and work for each process (kJ ),
(c) evaluate the thermal efficiency.
A heat pump maintains a dwelling at 70 F when the outside
temperature is 40 F. The heat transfer rate through the walls and
roof is 1300 Btu/hr per degree temperature difference. Determine
the minimum theoretical power required to drive the heat pump
(hp).
C l a u s i u s E q u a l i t y
Consi der a Carnot heat engi ne wi th no external
i rreversi bi l i ti es:
F or a f i xed heat i nput:
W W Q Q
R I C R C I
> <
, ,
F or the reversi bl e cycl e:
Q
Q
T
T
Q
T
Q
T
H
C
H
C
H
H
C
C
= =
T hus, for a reversi bl e cycl e
QH
QC
H igh T emperature
Reservoir at T H
L ow T emperature
Reservoir at T C
H eat
E ngine /
Pump
W= QH -QL
Q
T
Q
T
H
H
C
C
= 0
Clausius Inequality
No real heat engine, heat pump, or refrigeration
cycle is reversible. Since QC,I>QC,R:
1. Power cycle
Q
T
Q
T
H
H
C
C
s 0
2. Refrigeration/heat pump cycle

Q
T
Q
T
C
C
H
H
s 0
In general:
oQ
T
cycle }
= s o 0
o
cycle
=0 implies an internally reversible system
o
cycle
>0 irreversible (real) cycle
o
cycle
<0 impossible
Now consider two reversible cycles composed of
processes A+C and B+C :
2
o o Q
T
Q
T
A C
|
\

|
.
| +
|
\

|
.
| =
} }
1
2
2
1
0
o o Q
T
Q
T
B C
|
\

|
.
| +
|
\

|
.
| =
} }
1
2
2
1
0
1
Thus:
} }
|
.
|

\
|
= |
.
|

\
|
1
2
2
1
B A
T
Q
T
Q o o
Since this integral is independent of path, it is a
property:
A
B
C
3
Entropy
For an internally reversible cycle:
dS
Q
T
rev
=
|
\

|
.
|
o
int
ds
q
T
rev
=
|
\

|
.
|
o
int
Thus for a closed system:
AS dS
Q
T
rev
= =
|
\

|
.
|
} }
1
2
1
2 o
int
(kJ /K)
As ds
q
T
rev
= =
|
\

|
.
|
} }
1
2
1
2 o
int
(kJ /kgK)
For a heat reservoir (constant temperature)
AS =Q
R
/T
R
For a closed system, all entropy changes are due to
heat transfer if process is internally reversible.
oQ dS > > 0 0
dS
Q
T
rev
=
|
\

|
.
|
o
int
oQ dS = = 0 0
oQ dS < < 0 0
Rearranging the definition of entropy
Q TdS
int rev
=
}
1
2
For an internally reversible C.S., the heat transfer is:
1
2
d s s 1 s 2
T 1
T 2
o Q = T d s
}
=
2
1
TdS Q
rev int
Example
A system executes a power cycle while receiving 2000 Btu by heat
transfer at a temperature of 1000 R and discharging energy by
heat transfer at a temperature of 500 R. There are no other heat
transfers. Find scycif the thermal efficiency is (a) 75%, (b) 50%,
and (c) 25%. Identify which cases are internally reversible,
irreversible, and impossible.
Entropy
For an internally reversible cycle:
dS
Q
T
rev
=
|
\

|
.
|
o
int
ds
q
T
rev
=
|
\

|
.
|
o
int
Units =kJ/K or kJ /kg-K
Thus for a closed system:
AS dS
Q
T
rev
= =
|
\

|
.
|
} }
1
2
1
2 o
int
(kJ /K)
As ds
q
T
rev
= =
|
\

|
.
|
} }
1
2
1
2 o
int
(kJ /kgK)
For a heat reservoir (constant temperature)
AS =QR/TR
Q T d S
i n t r e v
=
}
1
2
4
Calculating S
1. Entropy definition
2. Tabulated data - You already know how to look up u, use the same technique to
look up s for superheated vapors and two-phase mixtures.
3. Entropy equations (Tdsequations)
4. Entropy graphs (T-s, h-s)
5. Approximations (with assumptions): Incompressible fluid, ideal gas
REMEMBER: Entropy IS a property and can be used to specify a substances
state!
d S
Q
T
r e v
=
|
\

|
.
|
o
i n t
T-ds Equations
Consider a simple, compressible, closed system
undergoing an internally reversible process:
o o q W du =
oq Tds =
ow pdv =
pdv du Tds + =
pv u h + =
vdp pdv du dh + + =
vdp dh Tds =
These equations relate properties so they are valid
for reversible or irreversible process, open or closed
systems.
THESE EQUATIONS ARE EXACT!!
Tds=dh-vdp
Example: Isobaric phase change, (p and T constant)
Tsat =
hg = kJ /kg
hf = kJ /kg
sg= kJ /kg K
sf = kJ /kg K
Calculate:
sg sf = kJ /kg K
(hg-hf)/Tsat= kJ /kg K
Tabulated Data Example
1 kg of H2O undergoes a process from 4 bar, 200 C to p2=1 bar.
During the process the specific entropy decreases by 3.1378 kJ /kg-
K. Find T2 and h2.
5
T-s Diagrams
T-s diagrams look very similar to T-v diagrams, and we will use
these to picture cycles and locate states.
Figure A.9
Figure A.10 (h-s diagram, Mollier diagram)
Approximations: Incompressible Substances
s ~ sf(T)
As =sf,2 sf,1
What assumption has been made?
Or
dv = 0
and du c T dT = ( ) .
ds
du
T
pdv
T
= + .
Thus,
As c T
dT
T
c
T
T
= ~
|
\

|
.
| }
( ) ln
1
2
2
1
What assumptions have been made?
When will these approximations be valid?
Incompressible example
A 1 kg copper bar (T=400 K) is dropped into a bucket of water
(T=300 K, m=20 kg). What is the net change in entropy for the
system? Is this process reversible? Why?
p v R T =
d u c d T
v
=
d h c d T
p
=
= + = + d s
d u
T
p d v
T
c
d T
T
R
d v
v
v
d s
d h
T
v d p
T
c
d T
T
R
d p
p
p
= =
( ) A s c
d T
T
R v v
v
= +
}
l n
2 1
1
2
( ) A s c
d T
T
R p p
p
=
}
l n
2 1
1
2
Approximation: Ideal Gas
Integrating we get the ideal gas entropy relations
6
( ) s T c
d T
T
p
T
=
}
0
c
d T
T
c
d T
T
c
d T
T
p p
T
p
T
1
2
0 0
2 1
} } }
=
( ) ( ) c
d T
T
s T s T
p
1
2
2 1 }
=
( ) ( ) ( ) A s s s s T s T R p p = =
2 1 2 1 2 1
l n
A s c
T
T
R
v
v
v
=
|
\

|
.
|
+
|
\

|
.
|
l n l n
2
1
2
1
A s c
T
T
R
p
p
p
=
|
\

|
.
|

|
\

|
.
|
l n l n
2
1
2
1
(a) Tabular Data
Define:
This is only a function of temperature, thus
Ideal gas entropy evaluation using tables:
(b) Constant specific heats
A s c
T
T
v
=
|
\

|
.
|
l n
2
1
A s c
T
T
p
=
|
\

|
.
|
l n
2
1
A s R
v
v
R
p
p
=
|
\

|
.
|
=
|
\

|
.
|
l n l n
2
1
1
2
(c) Special cases
Isochoric process:
Isobaric process:
Isothermal process (pv =c):
Examples
Find the change in entropy between these states:
water, p1=10Mpa, T1=400 C, p2=10 Mpa, T2=100 C
R134-a, h1=111.44 kJ /kg, T1=-40 C, p2=5 bar, x2=1
Air, T1=7 C, p1=2 bar, T2=327 C, p2=1 bar
Hydrogen, T1=727 C, p1=1 bar, T2=25 C, p2=3 bar
Examples
0.0242 kg of air undergoes a cycle consisting of the following
processes:
1-2 constant-volume heating at V=0.02 m
3
from p1=0.1 Mpato
p2=0.42 Mpa
2-3 constant-pressirecooling
3-1 isothermal heating
Assuming cp=1 kJ /kg-K, evaluate the change in entropy for each
process. Sketch the cycle on p-V and T-s diagrams
7
Entropy Balance: Closed Systems
Recall the ClausiusInequality:
=0 implies an internally reversible system
>0 irreversible (real) cycle
<0 impossible
Recall the definition of entropy:
0 s
}
T
Q o
o Q
T
c y c l e }
= o
o
c y c l e
o
c y c l e
o
c y c l e
d s
q
T
r e v
=
|
\

|
.
|
o
i n t
Consider a closed systemcycle
ClausiusInequality:
Since entropy is a property As
12
=-As
21
independent of irreversibilities.

I
R
1
2
0
1
2
int
2
1
s = |
.
|

\
|
+ |
.
|

\
|
=
} } }

I
rev
T
Q
T
Q
T
Q
o
o o o
21
2
1
int
1 2 12
s
T
q
s s s
rev
A = |
.
|

\
|
= = A
}

o
Thus for closed systems:
Entropy Entropy Entropy
Change(+/-) Transfer(+/-) Production(+)
Adiabatic process: =o
Adiabatic and internally reversible process:
A S S S
Q
T
= =
|
\

|
.
| +
} 2 1
1
2 o
o
A S > 0
A S = 0
Increase Of Entropy Principle
By combining a system and its surroundings
we can create an isolated system (universe)
This is an alternate statement of the second law:
1. Entropy of the universe always increases (Entropy production
represents a degradation in potential to do work)
2. A spontaneous process must increase entropy. At equilibrium,
entropy is maximized
3. Higher entropy states are more probable in nature
System
Surroundings
0 > = + = A
}
o o
o
T
Q
S
isol
A A A S S S
i s o l s y s s u r r
= + = > o 0
8
Examples
An insulated piston-cylinder assembly contains R134-a, initially
occupying 0.6 ft3 at 90 psi and 100 F. The refrigerant expands to
a final state where the pressure is 50 psi. The work developed by
the refrigerant is measured as 5 Btu. Can this value be correct?
1-lbm of air in a piston-cylinder device is compressed adiabatically
from 40 F, 1 atmto 5 atm.
If the air is compressed reversibly, determine the temperature at the
final state (F) and the work required (Btu)
If the compression requires 20% more work than in part a, determine
the temperature (F) and the amount of entropy produced (Btu/ R)
Sources of Entropy Production
(1) Internal irreversibilities
For a cycle:
s is the internal entropy production from friction and nonquasistatic
processes (dissipation)
For a Carnot Engine (o =0)
A S
Q
T
i
i i
= + =

o 0
=
|
\

|
.
|
o
Q
T
Q
T
H
H
C
C
Q
T
Q
T
H
H
C
C
=
(2) External Irreversibilities
For a systemcomprising no mass, but only heat transfer, As=0
Irreversible
Reversible
Impossible
(violation of ClasiusStatement)

TA
TB
Q o
o
+ = A
}
T
Q
S
0
1 1
>
|
|
.
|

\
|
= + =
A B B A
T T
Q
T
Q
T
Q
o
T T
A B
>
T T
A B
=
A B
T T >
Second Law For Closed Systems
(1) Internally Reversible Process
(2) Adiabatic Process
Irreversible
Reversible
Thus a reversible, adiabatic process is isentropic.
(3) Isolated System
A S S S
Q
T
= =
|
\

|
.
| +
} 2 1
1
2 o
o
A S
Q
T
=
|
\

|
.
|
}
o
i n t r e v
1
2
Q T d S
i n t r e v
=
}
1
2
A S > 0
A S = 0
A A A S S S
i s o l s y s s u r r
= + = > o 0
9
Example
An electric motor operating at steady state draws a current of 10 A
with a voltage of 220 V. The output shaft rotates at 1000 RPM
with a torque of 16 N-m applied as an external load. The rate of
heat transfer from the motor to its surroundings is related to the
surface temperature Tb and the ambient temperature To by
Q=hA(Tb-To), where h=100 W/m2-K, A=0.195 m2, and To =293
K. Determine the temperature Tb (K). For the motor as the
system, determine the rate of entropy production (kW/K).
Second Law For Open Systems
Second law: The change in entropy for a system is equal to the
entropy transferred into the system minus the entropy transferred
out of the system plus the entropy produced by the system
For closed systems
For open systems entropy is also brought in and carried out by mass
transfer (just like energy) so
Note that entropy production is now an entropy production rate
CV
e
e e
i
i i
CV
T
Q
s m s m
dt
dS
o
o

+ + =
}
12 1 2 12
o
o
+ = = A
}
T
Q
s s s
Special Cases (assumptions)
1. Steady state:
Entropy is a property so it does not vary with time
2. One inlet/one outlet:
or dividing by mass flow rate
This is very similar to the closed-system form
CV
e
e e
i
i i
T
Q
s m s m o
o

+ + =
}
0
( )
CV i e
T
Q
s s m o
o

+ =
}
m T
q
s s
CV
i e

o o
+ =
}
3. Heat transfer at constant temperature:
4. Adiabatic
5. Adiabatic and Reversible
or s
2
=s
1
So, for a steady state, 1-inlet/1-outlet, adiabatic, and reversible control volume, the
change in entropy is zero (isentropic)
Isentropic processes have a special use in defining efficiencies (later)
A s
q
T m
C V
= +

o
A s
m
C V
=

o
A s = 0
10
Open Systems Review (Governing Equations)
This is the heart of ME 2233!
Conservation of Mass:
Conservation of Energy (1st law):
Entropy Balance (2nd law):
Closed system equations result from

=
exits
e
inlets
i
cv
m m
dt
dm


+ + + + + =
exits
e
e
e e
inlets
i
i
i i
cv
gz
V
h m gz
V
h m W Q
dt
dE
)
2
( )
2
(
2 2


0 = m
CV
e
e e
i
i i
CV
T
Q
s m s m
dt
dS
o
o

+ + =
}
Examples
An inventor claims to have developed a device requiring no work
input or heat transfer, yet able to produce at steady state hot and
cold air streams as shown in the figure. Employing the ideal gas
model for air and ignoring kinetic and potential energy effects,
evaluate this claim.
Methane at 280 K, 1 bar enters a compressor operating at steady state
and exits at 380 K, 3.5 bar. Ignoring heat transfer with the
surroundings and employing the ideal gas model with cp(T) from
Table A-21, determine the rate of entropy production within the
compressor (kJ /kg-K).
Examples
The figure shows a proposed device to develop power using energy
supplied to the device by heat transfer from a high-temperature
industrial process together with a steam input. The figure provides
data for steady-state operation. All surfaces are well insulated
except for the one at 527 C, through which heat transfer occurs at a
rate of 4.21 kW. Ignoring kinetic and potential energy, evaluate
the maximum theoretical power that can be developed (kW).