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mgh
A rock spontaneously rises by lowering
its temperature such that mCpT = mgh
so that U = 0.
work out W
.
heat in
Q1
Applying the first law to the operation of the machine or engine, W = Q1Q2
where Q2 corresponds to any heat rejected from the engine,
Q Q2
Q
Q1
1
1 2
Q1
Q1
Heat engine
system
Q2
Carnot Cycle
The Carnot cycle is a reversible cycle operating between two temperatures.
A B: Isothermal expansion adsorbing heat Q1.
B C: Adiabatic expansion decreasing T from T1 to T2.
C D: Isothermal compression rejecting heat Q2.
D A: Adiabatic compression increasing T from T2 to T1.
T1
A
Q1
T1
D
Q2
Q1
T2
T2
Q2
Q2
Since all the steps are reversible U = 0, W = Q1 - Q2 and 1
Q1
3
Clausius Statement
Carnots Theorem:
No engine operating between two given reservoirs can be more efficient than a
Carnot engine operating between the same two reservoirs.
4
QH1
C
WH = QH1 - QH2
QH2
QC2
T2
W
WH
C .
QH 1 QC1
Since the Carnot engine is reversible we can drive it backwards using the
mechanical energy from H. The Carnot cycle can be adjusted (adiabats) so
that in one cycle it uses exactly as much work as H produces.
WC WH and therefore QC1 QH 1 .
QH1
C
Composite
Engine
WH = QH1 - QH2
QH2
QC2
T2
This is a violation of the Clausius statement
of the second law!
Qn+2
Cn+2
Q1
f T1 ,T2 .
Q2
Tn+2
Wn+2
Qn+1
Tn+1
Wn+1
Cn+1
Qn
Cn
Tn
Qn 2
f Tn 2 ,Tn 1
Qn 1
Qn 1
C n 1 :
f Tn 1 ,Tn
Qn
Qn
Cn :
f Tn ,Tn 1
Qn 1
Wn
Qn-1
Tn-1
Qn+2
Cn+2
Tn+2
Wn+2
Qn+1
Tn+1
Wn+1
Cn+1
Qn
Cn
Tn
Wn
Qn-1
Tn-1
Qn 2
f Tn 2 ,Tn 1
Qn 1
Then,
f Tn 2 ,Tn 1 f Tn 2 ,Tn 1 f Tn 1 ,Tn f Tn ,Tn 1
This can only be true if the fs factorize such that
f Tn 2 ,Tn 1
f Tn 2 Tn 2
f Tn 1 Tn 1
Qn 2 Tn 2
According to Carnots theorem and its corollary we can make the following statements:
reversible
Q2
Qr 2
1
1
Q1
Qr1
Q2 Qr 2 T2
Q1 Qr1 T1
Q2 T2
Therefore
. Taking the heat entering the system as positive, we can say
Q1 T1
Q1 Q2
Q
Q
Entropy
def:
We can now define a new variable, the entropy S, by the relation
dS =
Qrev
Qrev.
.
T
1
2
S 2 S1
10
Q A Q
T Brev . T
Airrev .
B
Q B Q
T Arev . T
Airrev .
B
i.e.,
Q
A T S B S A ,
rev .
B
But
Q
SB S A ,
T
Airrev .
B
or
dS
Q
.
T
dS 0
dU Q W 0
dU TdS pdV 0
W RT ln V2 / V1 RT ln p1 / p2
S system R ln V2 / V1
S system R ln V2 / V1
13
P1, V1
Diathermal Walls
S resevoir Stotal Q / T W / T
Reservoir (T)
P, T1
dS system
Adiabatic Walls
DQ
Any Reversible Path
T
Q C p dT
T2
C p dT
T1
dS system
14
T2
C p ln 0.
T1
Examples
An inventor claims to have developed
a power cycle capable of delivering a
net work output of 410 kJ for an energy
input by heat transfer of 1000 kJ. The
system undergoing the cycle receives
heat transfer from hot gases at
T = 500 K and discharges energy by
heat transfer to the atmosphere at
T = 300 K. Evaluate this claim.
The thermal efficiency is
Wcycle
QH
410 kJ
0.41
1000 kJ
QC
T
300 K
1 C 1
0.40
QH
TH
500 K
No good!
15
16
Entropy Production
X
Q B Q
T Arev . T
Airrev .
Q
SB S A ,
T
Airrev .
A
x
Determination of the change in
entropy for an irreversible change
Recall the determination of entropy
change for an irreversible process.
Q
Q
T Brev . T
Airrev .
B
It is convenient to define a
quantity such that
Q A Q
T Brev . T
Airrev .
B
Def:
is necessarily a positive
quantity called entropy
production.
17
Entropy Production
Rewriting the expression
Q A Q
T Brev . T
Airrev .
B
we obtain,
Q
S A S B
T
Airrev .
B
T
Airrev .
B
S A SB
Q
{
T
entropy
Airrev .
1 2 3 production
B
SB S A
14 2 43
entropy
change
entropy
transfer
18
Entropy Production
can not be less than zero
By contrast the change in the entropy
of the system can be positive, negative
or zero:
0
SB S A : = 0
<0
Qj
Tj
19
Examples
Water initially a saturated liquid at 100 C is contained in a piston cylinder assembly.
The water undergoes a process to the corresponding saturated vapor during which the
piston moves freely in the cylinder. If the change of state is brought about by heating
the water as it undergoes an internally reversible process at constant pressure and
temperature determine the work and the heat transfer per unit of mass in kJ/kg
W
p vg v f 170 kJ/kg Table A-2
m
20
Examples
Since the process is reversible and occurs at constant temperature
g
Q TdS mT sg s f
f
Q
T sg s f 2257 kJ/kg
m
This could also have been calculated our old way
ug u f
Q W
m m
Q
u g u f p vg v f hg h f
m
21
Examples
The figure shows a system receiving heat
Q from a reservoir. By definition the reservoir
is free of irreversibilities, but the system is not,
fluid friction, etc. Lets determine the
entropy change of the system and that of the
reservoir.
For the system,
S 2 S1
Tb
Qres
Q
0
Tb
Tb
22
Examples
Water initially a saturated liquid at 100 C is contained in a piston cylinder assembly.
The water undergoes a process to the corresponding saturated vapor during which the
piston moves freely in the cylinder. There is no heat transfer with the surroundings.
If the change in state is brought about by the action of a paddle wheel, determine the
net work per unit mass in kJ/kg and the amount of entropy produced per unit mass in
kJ/kg-K.
As the volume of the system increases during this process, there is an energy transfer
by work from the system during the expansion as well as an energy transfer by work
to the system done by the paddle wheel. The net work is evaluate from the change
in internal energy.
23
Examples
From the 1st Law, U = -W.
On a unit mass basis we have,
W
u g u f 2087.56 kJ/kg
m
The minus sign indicates that the work input by stirring is greater in magnitude than the
work done by the water as it expands.
The entropy produced is evaluated by applying the entropy balance,
Q
0
1 T
S
On a unit mass basis,
sg s f 6.048 kJ/kg-K
m
24
Entropy Diagrams
isentrop
isenthalp
isochor
isobar
isotherm
25
Entropy Diagrams
T
CW power cycle
S
Carnot cycle on a T S
diagram.
26
Thermodynamic Potentials
Combined 1st and 2nd Law
dU = TdS - pdV
U U S ,V
U
dS
S V
p -
S V
dU
U
dV
V S
U
T
p
, -
V S V S S V
dH
H
H
,
V
T
V
p S S p
p
T p
dG
G
S
G
V
,
,V
T p
p T27 p T T p
T V
V T V T T V
dA
dU = TdS - pdV
dH = TdS + Vdp
dG = Vdp - SdT
dA = -pdV - SdT
The appropriate thermodynamic potential
to use is determined by the constraints
imposed on the system. For example,
since entropy is hard to control (adiabatic
conditions are difficult to impose) G and A
are more useful. Also in the case of solids
p is a lot easier to control than V so G is
the most useful of all potentials for solids.
28
T2
T1
T1
S S T dT C p T d ln T
T2
S T2 S T1 C p T d ln T
T1
G G T2 G T1 T2 T1 S T1 dT C p T d ln T
T
29
T1
1
T2
T2