4200:225 Equilibrium

Thermodynamics
Unit I. Earth, Air, Fire, and Water
Chapter 4. Thermodynamics of Processes
By J.R. Elliott, Jr.
Thermodynamics I. Energy and Entropy Slide 1
I. Energy and Entropy
The Carnot Cycle
Condenser
Boiler
W
T
W
p
Q
H
Q
L

T
S
1 2
3 4
LIQUID
VAPOR
W/Q
H
General Formula for the Thermal Efficiency
Entire process is reversible: S
11
=0
+
Q
T
Q
T
O Q
T
T
Q
H
H
L
L
L
L
H
H
But -W=Q
H
+ Q
L
= Q
H
(1-T
L
/T
H
)

W
Q
T T
T
H
H L
H
Control efficiency by controlling temperature difference.
Thermodynamics I. Energy and Entropy Slide 2
I. Energy and Entropy
The Basic Rankine Cycle
Condenser
Boiler
W
T
W
p
Q
H
Q
L
T
S
1
2
3 4
LIQUID VAPOR
SUPERCRITICAL
Advantages:
1. Less wear on turbine and compressor.
2. Compression of liquid is cheap and easy (negligible in most cases).
Disadvantages:
1. Lower thermodynamic efficiency than Carnot or Stirling. This can be somewhat
compensated by multiple stages and regeneration.
Thermodynamics I. Energy and Entropy Slide 3
Example 4.1 Power plant based on the ordinary Rankine cycle
The steam power installation in a chemical plant must satisfy the following requirements:
1) 500C maximum temperature from the boiler.
2) 0.025MPa saturated vapor from the turbine.
3) 1 MW net power output.
Determine:
a) The operating pressure of the boiler
b) The thermal efficiency
c) The circulation rate
Boiler
Condr
T1
a) Flow Sheet
p
5
6
3
4

T
S
b ) T - S D i a g r a m
5
1
2
4
6
3
a) Interpolating on the pressure at 500C and S=7.8314, P = 0.869 Mpa
b) The enthalpy at state 3 is interpolated at 500C and 0.869MPa, H = 3480
W
T
= 2618-3480 = -862 J/g; W
p
= VdP = VP = 0.79 J/g
W
net
= W
T
+ W
p
= -861 J/g; Q
L
= 2618 - 273 = 2345; = 861/(2345+861) = 27%
Thermodynamics I. Energy and Entropy Slide 4
Example 4.3. Power plant based on a Rankine cycle with reheat
Boiler
Condr
T1 T2
7
8
3
4
5
6

T
S
7
1
2
3
4
5
6
8
Consider the same outlet conditions as above, but interject an extra stage for the pressure
drop. That is, consider the case depicted above with stream 3 being at 434C and 6MPa
and stream 5 at 500C and 0.8 MPa. Compute the thermal efficiency in this case.
434C, 6MPaH
3
= 3262 J/g; S
3
= 6.6622 J/g-K; State 4 is SatV, 0.8MPa H
4

= 2769
State 5 is same as previous problem H
5
= 3480 J/g, H
6
= 2618 J/g, H
7
= 272.
The pump work has increased because the pressure has increasedW
p
= 6 J/g, H
8
= 278
W
net
= (H
4
-H
3
) + (H
6
-H
5
) + W
p
= (2769-3262)+(2618-3480) + 6 = -1349
Q
tot
= (H
3
-H
8
) + (H
5
-H
4
) = (3262-278)+(3480-2769) = 3695 J/g
= 36.7 %
This compares to 27% for the cycle without reheat.
Note: The Carnot cycle gives the upper limit of
carnot
= (500-65)/773 = 56%
Thermodynamics I. Energy and Entropy Slide 5
I. Energy and Entropy
Refrigeration
COP = Q
L
/W
net
For Carnot: COP = (Q
H
/W
net
)*(Q
L
/Q
H
) = T
L
/(T
H
-T
L
)
But the Carnot cycle is not always practical.
Therefore, we apply the ORDINARY VAPOR COMPRESSION (OVC) CYCLE
Condenser
Evaporator
W
P
Q
H
Q
L
Throttle

T
S
4
3
2
LIQUID
VAPOR
SUPERCRITICAL
1
COP for ordinary vapor compression cycle
COP = Q
L
/W; Q
L
= (H
2
-H
1
)
Energy balance: W = H
23
= (H
3
-H
2
)
COP = (H
2
-H
1
)/(H
3
-H
2
) = (H
2
-H
4
)/(H
3
-H
2
)
Thermodynamics I. Energy and Entropy Slide 6
I. Energy and Entropy
Example 4.5 Refrigeration by vapor-compression cycle
A cold storage room is to be maintained at -15C and the available cooling water exits
the evaporator at 298K. The refrigerant temperature exiting the condenser is to be 30C.
The refrigeration capacity is to be 120,000 Btu/hr (126,500 kJ/hr). (This is the cooling
rate required to freeze ten tons of 32F water to 32F ice in a 24 hr period. It is known in
the trade as ten tons of refrigeration.) Freon-134a will be used for the vapor
compression cycles. Calculate the COP and recirculation rate (except part a for the
following cases:
a) Carnot cycle
b) Ordinary vapor compression cycle.
c) Vapor compression cycle with
expansion engine
d) Ordinary vapor compression cycle
for which compressor is 80% efficient.
(a) Carnot
COP =
( ) ( )
06 . 5
253 303
253

L H
L
T T
T
State H S Comment
1 241.5 --- Throttle from 4
1 235.0 1.1428 Tur from 4, q=.29
2 386.5 1.7414 Sat V, 253K
3 424 1.7414 S
3
=S
2
, read chart
4 241.5 1.1428 Sat L, 303K
Thermodynamics I. Energy and Entropy Slide 7
(b) OVC cycle
( )
( )
( )
( )
87 . 3
5 . 386 424
5 . 241 5 . 386
2 3
4 2
2 3
1 2

H H
H H
H H
H H
COP
=
126,500
386.5- 241.5
= 872
kg
hr
&
m
(c) VC cycle with turbine expansion
qS
1
V
+ (1-q) S
1
L
= S
4
L
= 1.1428 = q(1.7414) + (1-q) 0.8994 q = 0.289 H
1
= 235
( )
( )
89 . 4
) 5 . 241 0 . 235 ( ) 5 . 386 424 (
0 . 235 5 . 386
) (
4

1 2 3
1 2

H H H H
H H
COP
rev
=
126,500
386.5- 235.0
= 835
kg
hr
&
m
(d) States (1), (2) & (4) are the same as in (b)
The only difference is that W = (424-386.5)/0.8 = 46.9

COP
H H
H H
2 4
3 2
3865 2415
46 9
309
. .
.
.
and m = 872 kg/hr
Note: Choice of refrigerant dictated by
(1) Toxicity (Freon-12, 22 are bad for
ozone and is being phased out)
(2) vapor pressure > atmospheric @ T
fridge
(3) vapor pressure not too high @ T
H
(4) high heat of vaporization per unit mass
(5) small Cp/Cv
(6) high heat transfer coefficients in vapor
and liquid
Thermodynamics I. Energy and Entropy Slide 8
I. Energy and Entropy
Example 4.6. Liquefaction of methane by the Linde process.
Natural gas, assumed here to be pure methane, is liquefied in a simple Linde process.
Compression is to 60 bar and precooling is to 300 K. The separator is maintained at a
pressure of 1 bar and unliquefied gas at this pressure leaves the cooler at 295 K.
Solution
Precool
Heat Exch
Throttle
Flash
Drum
Compressor
1
2 3
4
5
6
7
8
a) Bottom half E-Bal: H
3
- [qH
8
+(1-q)H
6
] = 0

q
H H
H H
H H SATL
H H SATL
=
3 6
8 6
300 1
1295 1
(60, ) ( , )
( , ) ( , )

1130 284
1195 284
0 9286 714% . . liquefied
b) E-Bal around HXER: H
4
-H
3
= q(H
8
- H
7
)
= .9286(1195-796.1)= -370.5
H
4
=780 @ 60 BAR chart gives 203K
Thermodynamics I. Energy and Entropy Slide 9
I. Energy and Entropy
Example 4.8 Thermal Efficiency of the Otto Engine
Determine the thermal efficiency of the air-standard Otto cycle as a function of the
specific heat ratio (= Cp/Cv) and the compression ratio r=V1/V2.
Solution:
QH = Cv(T3-T2)
QL = Cv(T1-T4)
W=QH+QL = Cv(T3-T2+T1-T4)
= Cv(T3-T2+T1-T4)/[Cv(T3-T2)] + 1-(T3-T2)/(T3-T2) =
1 + (T1-T4)/(T3-T2)
Cv R Cv R Cv R
V
V
V
V
T
T
V
V
T
T
/
1
2
/
4
3
3
4
/
2
1
1
2
;

,
_

,
_

,
_

T
4
= T
3
r
-R/Cv
; T1 = T2 r
-R/Cv
= 1 - r
-R/Cv
= 1 - r
(1-)
Thermodynamics I. Energy and Entropy Slide 10
I. Energy and Entropy
In a large refrigeration plant it is necessary to compress a fluid which we will assume to
be an ideal gas with constant heat capacity, from a low pressure P1 to a much higher
pressure P2. If the compression is to be done in two stages, first compressing the gas
from P1 to P*, then cooling the gas at constant pressure down to the compressor inlet
temperature T1, and then compressing the gas to P2, what should the value of the
intermediate pressure be to accomplish the compression with minimum work?
Solution:
E-Bal:
H=Q+W=W=CpT
S-Bal: S=0 T
*
/T
1
= (P
*
/P
1
)
R/Cp
; T
2
/T
1
= (P
2
/P
*
)
R/Cp
W
tot
= Cp(T
2
-T
1
) + Cp(T*-T
1
) = CpT
1
{[(P
2
/P
*)
R/Cp
- 1] +
[(
P
*
/P
1
)
R/Cp
- 1]
To maximize function, set derivative to zero.
0
/ /
/
1
*
*
/
*
2
*
1
*

'

,
_

,
_

Cp R
Cp R
P
P
P
Cp R
P
P
P
Cp R
CpT
dP
dW
Note: Equal compression ratios per stage is optimal for multistage compressors also.
1 2
*
/
1
*
/
*
2
P P P
P
P
P
P
Cp R
Cp R

,
_

,
_