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Outline
Outline
Introduction
Concept
Property
Defined
Zeroth Law
Thermal equilibrium
Temperature
First Law
Energy conservation
Energy
Second Law
Direction of processes
Entropy
(page 153)
A heat engine is a
system that converts
thermal energy
(transferred as heat)
into mechanical energy
(transferred as
work).
Examples: Otto cycle,
Diesel cycle, Rankine
steam cycle (Chapter 8).
Hot Reservoir
QH
A Cyclic
Process
(Heat Engine)
W = QH QL
QL
Cold Reservoir
Thermal reservoir:
Fig. 7.3: Sketch of a system that violates the Kelvin form of the Second Law of Thermodynamics
Clausius statement:
It is impossible for a
cyclic process to
transfer the heat
absorbed from a
body at a low
temperature to a
body at a higher
temperature
without producing
any other effects.
https://en.wikipedia.org/wiki/Combustion
http://www.theguardian.com/science/2011/apr/28/wellcome-science-writing-prize
https://physics.aps.org/story/v22/st5
http://phys.org/news/2013-03-unusual-recrystallization-behavior-one-dimensional-electron.html
Process A is a
contradiction of
the Kelvin form of
the Second Law.
The work from
Process A is used
to drive Process B.
Fig. 7.5: Sketch of a system showing that failure of the Kelvin statement implies failure
of the Clausius statement
If it were possible, it
would be in contradiction
of the Kelvin form of the
Second Law.
Fig. 7.6: Sketch of a system showing that failure of the Clausius statement implies
failure of the Kelvin statement
Pexternal
Pile of
sand
Forward
Process
Pexternal
Reverse
Process
P1
P1
P2
P1
(page 159)
P1 > P > P2
P2
P2
Pexternal
Forward
Process
Pexternal
Weight
Reverse
Process
P1
P1
P2
P1
P2
P2
P2
(page 159)
frictional effects
unrestrained expansion
mixing of fluids
electric resistance
chemical reactions
heat transfer across a finite temperature difference
http://www.learnthermo.com/T1-tutorial/ch06/lesson-D/pg07.php
(page 159)
http://www.industrialboiler.com/boilers/watertube-boilers.aspx
http://www.power-eng.com/articles/print/volume-117/issue-10/features/converting-once-through-cooling-to-closed-loop.html
http://peakoil.com/consumption/watering-down-the-energy-debate
2.
3.
4.
(page 160)
Hot Reservoir
QH
A Cyclic
Process
(Heat Engine)
W = QH QL
heat input
QH
(7.1)
(7.2)
(page 161)
QH QL
QH
QL
QH
(7.3)
(page 162)
Reversible Isothermal
Expansion at TH (1-2):
2. Reversible
4. Reversible Adiabatic
(page 162)
Compression (4-1):
(page 162)
P
1
QH
QH
2
TH
Wnet,out
TH
Wnet,out
4
3
TL
4
QL
Green area:
Work done by gas (Steps 1-3)
TH
Wnet,out
4
QL
QH
QL
TL
TL
v
Purple area:
Work done on gas (Steps 3-1)
Blue area:
Work done by cycle
(page 162)
in
(page 163)
Carnots Theorem:
No heat engine operating between two heat reservoirs can
have a higher thermal efficiency than that of a Carnot engine.
(page 163)
W
W
QH
QH
QH QH
QL QL
(page 163)
QL
QH
f TL , TH
(7.4)
QH
QL
g TL , TH
1 f TL , TH
Engine B:
QL
QF
g TF , TL
Engine C:
QH
QF
g TF , TH
Dividing:
QH
QL
(7.6c)
g TF , TH
g TF , TL
1
g TL , TH
1 f TL , TH
QL
TL
(7.5)
(7.7)
V2
RTH ln
V1
V3
QL RTL ln
V4
(7.8a)
(7.8b)
QH
QL
TH lnV2 V1
TL lnV3 V4
(7.9)
TH
TH
TL
TL
c v dT
V3
ln
R T
V2
(7.10a)
c v dT
V4
ln
R T
V1
(7.10b)
V3
V2
ln ln
V4
V1
(7.11)
From (7.9):
QH
QL
TH lnV2 V1
TL lnV3 V4
QH
QL
TH
TL
(7.12)
rev 1
QL
QH
TL
1
TH
(7.13)
rev 1
QL
QH
TL
1
TH
(7.13)
Engine A
Engine B
300 K = 27C
300 K = 27C
25%
62.5%
Hot Reservoir
QH
A Cyclic
Process
(Heat Engine)
QL
Cold Reservoir
W = QH QL
Hot Reservoir
QH
QH
Boiler, T<TH
A Cyclic
Process
(Heat Engine)
W = QH QL
Wnet ,in
Wnet,out
Pump
Turbine
Condenser, T>TL
QL
3
QL
Cold Reservoir
(page 171)
Boiler, T<TH
Wnet ,in
Wnet,out
Pump
Turbine
Condenser, T>TL
3
QL
(page 171)
(page 172)
(7.14)
Heat Pump
COPR
QL
Wnet ,in
COPHP
QH
Wnet ,in
COPR
QL
QH QL
COPHP
QH
QH QL
COPR
1
QH / QL 1
COPHP
1
1 QL / QH
(page 172)
1
COPR
QH / QL 1
COPR,rev
TH TL 1
(7.12)
TL
Heat Pump
COPHP
1
1 QL / QH
COPHP,rev
1 TL / TH
(page 173)
(page 175)
TH
TL
QL
TL
(7.12)
(7.22)
heat in (+)
heat out ()
QH QL
TH
TL
(7.23)
QH QL
0
TH TL
(7.24)
(page 175)
0
TH
TL
(7.25)
(7.26)
(page 175)
dQ dW 0
(5.1)
(page 175)
dS
dQrev
T
dQrev
S
T
1
(7.28)
(page 176)
2
S
1
(7.28)
dQrev
T
dQrev = 0 and S = 0
Such a process is called isentropic (constant entropy)
Although such processes cannot exist in reality, they provide a
convenient basis for efficiency calculations.
dQrev
Qrev
1
S
dQrev
T
Tconstant 1
Tconstant
1
Qrev
S
Tconstant
(7.29)
(page 176)
(page 177)
Q
S H
TH
Q
S L
TL
Total, Stotal
S total
Q
Q
T TL
Q H
TH T L
T H TL
(page 177)
vacuum
(page 177)
increasing entropy
http://chemwiki.ucdavis.edu/Textbook_Maps/General_Chemistry_Textbook_Maps/Map%3A_Lower's_Chem1/
07%3A_Solids_and_Liquids/7.1%3A_Matter_Under_the_Microscope
(7.33)
where
http://en.wikipedia.org/wiki/Ludwig_Boltzmann
(page 177)
Review:
The state of a single-phase,
single-species (pure) system
can be fixed by specifying
two (2) intensive variables
P2
Area w12 P dv
1
qrev Tds
dv
Adiabatic
reversible
(7.35)
(7.36)
v1
v2
(7.27)
P1
dQrev
T
dq
ds rev
T
dS
1
h
h'
Adiabatic
irreversible
2
2'
s
s
Note that S = 0
(7.37)
dQrev TdS
(7.38)
Therefore,
dU TdS PdV
(7.39)
T
T
or
du Pdv
ds
T
T
(7.40)
Substituting dH = dU + d(PV)
dS
T
T
T
T
dH VdP
dS
T
T
or
dh vdP
ds
T
T
(7.41)
dv = 0 and c = cv = cp
ds
du Pdv c dT
T
T
T
(7.42)
c dT
dT
T2
s
cave
cave ln
T
T
T1
1
1
(7.44)
T2
T1
T
T
cv dT Rdv
ds
T
v
cv dT
Rdv
s
T
v
1
1
(7.47b)
dh vdP
T
T
ds
c p dT RdP
T
P
T2
P2
s c p , ave ln R ln
T1
P1
(7.49b)
k 1
(7.50a)
T2
P2
c p , ave ln R ln
T1
P1
T2
P2
c p , ave ln c p , ave cv , ave ln
T1
P1
T
P
k ln 2 k 1 ln 2
T1
P1
T2 P2
T1 P1
k 1
k
(7.50b)
(page 186)
= + +
= + +
= + +
(page 186)
= + +
Integrating,
(7.55)
(page 186)
(page 189)
(page 189)
On a continuous basis:
dSsystem
Sin Sout S gen
dt
(7.59)
(7.60)
(page 189)
S heat
T
(7.61)
(page 189)
Sgen = 0
Sgen > 0
Sgen < 0
(page 190)
(7.59)
Q k
S system
S gen
Tk
(7.66)
(7.67)
surroundings
Q
Ssystem
Tsurroundings
(7.68)
(page 190)
sair
T2
P2
cP ln R ln
T1
P1
(page 191)
At steady-state,
0
dS system
dt
dSsystem
Q k
m i si m e se Sgen
dt
Tk
S gen
Q k
m e se m i si
Tk
(7.70)
(page 192)
Lost work
(page 192)
Turbine
(page 193)
S gen
Q k
m e se m i si
0
Tk
(7.72)
Q T m e se m i si
(7.74)
(page 193)
ue2
ui2
m e he gze m i hi gzi T m e se m i si Wideal
2
2
Wideal
ue2
ui2
T m e se m i si m e he gze m i hi gzi
2
2
(page 193)
net
work
output
(7.79b)
thermodynamic
g
ideal work output
(page 194)
W act
(7.80)
m h
Q m h m h
e e
i i
i i
m s m s m h m h
e e
i i
e e
i i
(page 194)
Wlost T m e se m i si Q
Recall that:
S gen
Q k
m e se m i si
Tk
T S gen T m e se m i si Q
Therefore:
Example 7.9
Wlost T S gen
(7.83)