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Entropy
Recall Carnot engine:
Hot Reservoir, TH
QH
W
QH
Cold Reservoir, TC
Recall Carnot equation:
QH
TH
QC
TC
QH QC
TH
TC
QH
QC
is negative:
Q H QC
0 (5.9)
TH TC
Recall: the principle characteristics of a property is that the sum of its change in a complete
cycle is zero.
Thus, eq 5.9 suggests the existence of a property whose changes are given by the quantities
Q/T.
64
Entropy
Consider reversible cyclic process shown in the following PV diagram:
QH
TH
P
TC
QC
V
We divide the path by a series of reversible adiabatic curves and isothermal curves. The
spacing of the isothermal steps is very close (infinitesimal) so that the heat quantities become
dQH and dQC so that eq. 5.9 becomes:
dQ H dQ C
0
TH
TC
dQ rev
0
T
(5.10)
(5.12)
65
Entropy
Consider arbitrary reversible paths from A to B:
D
B
P
A
C
V
dQ rev
t
dan S
T
ACB
t
The entropy changes: S
ADB
dQ rev
T
dQ rev
0)
T
Therefore:
St is independent of path and St = property change given by (StB - StA).
If A to B is irreversible, the entropy change must still: St = StB - StA (because S is a state
function). However, St is not given by dQ/T evaluated for irreversible process.
The entropy changes of a heat reservoir is always given by Q/T, because the effect of the
heat transfer is the same regardless of the temperature of the source or sink of the heat.
When a process is reversible and adiabatic, dQrev =0
process is said to be ISENTROPIC
dQ
T
66
Entropy
St of a system caused by the transfer of heat can always be calculated by S t
dQ
T
dU = dQ + dW
dU = (dQrev P dV)
dH = (dQrev P dV ) + P dV + V dP
dQrev = dH V dP
Recall
dQ rev
dS
T
ig
C dT dP
1 dQ rev
P
R
T
R T
P
ig
dS C P dT
d ln P
R
R T
ig
C P dT
S
P
T
ln
T
R
Po
o R T
(5.13)
(5.14)
ig
Recall that for ideal gas: Cp = A + BT + CT2 + DT2
Combining the two equations, the first term of RHS can be expressed as:
ig
T C P dT A ln BT CT 2 D
T
0
o
0 R T
2 To2
1
1
2
(5.15)
where T
o
Define mean heat capacity: Cig
P
T ig
To C P dT / T
ln T To
S
(5.16)
67
Entropy
ig
T CP dT
S To R T
R
ln
ig
CP
Divide 5.16 by R:
Recall:
ig
T C P dT A ln BT CT 2 D
T
0
o
0 R T
2 To2
1
1
2
(5.16a)
(5.15)
ig
CP
Recall: Cig
P
S A BT CT 2 D
0
o
R
2 To2
1 1
2 ln
T ig
To C P dT / T
ln T To
S
(5.16)
dT
ig
T ig
Rearrange: T C P T C P ln T
o
S
o
Divide by R:
ig
T C P dT
T
o R T
(5.17)
ig
CP
R
S ln T
To
ig
C
Recall S T P dT ln P
To R T
R
Po
(5.16b)
(5.16c)
(5.14)
ig
CP
R
S ln T ln P
To
Po
(5.18)
68
Entropy
Mathematical Statement of The Second Law
Consider:
TH
QH
TC
Entropy change at hot reservoir:
t Q
S H
TH
t Q
SC
TC
t S t Q Q
STotal SH
C T
H TC
T T
STotal Q H C
TH TC
69
Entropy
Qrev
Reversible
path
P
A
Irreversible
adiabatic
B
V
If A-B process results in an entropy change, then there must be heat transfer during B-A
process that:
t S t A dQ rev
S t SA
B B T
t St
SA
B
is also negative
t St
SB
A
(5.19)
70
Entropy
Recall:
Hot Reservoir, TH
QH
QH
Cold Reservoir, TC
STotal
Work of the engine:
W Q H QC
QH
TH
QH
TC
W
1
1
)
TC TH
TC
QH
TH
QH
TH
t
and SC
QC
TC
QC
TC
QC Q H W
STotal
QH QH W
TH
TC
W
TC
or
T
W TC STotal Q H 1 C
TH
TC
Recall: W TC STotal Q H 1
TH
71
Entropy
Hot Reservoir, TH
QH
QH
Cold Reservoir, TC
T
Recall: W TC STotal Q H 1 C
TH
Minimum work = 0 (completely inefficient, the system become simple irreversible heat
transfer between TH and TC)
T
0 TC STotal Q H 1 C
TH
T T
STotal Q H H C
TH TC
T
W 0 Q H 1 C
TH
T
W Q H 1 C
TH
CP
CP
g
S dT H f T
t dT H T
dT
T
T
T
Tf
T
T
T
f
CP
72