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Occurs if:
• change is made sufficiently quickly
• and/or with good thermal isolation.
Governing formula:
g
PV = constant
where g = CP/CV
Adiabat
P
Isotherms
1) Adiabatic: dQ = 0 = dU + dW
= dU + PdV
2) U only depends on T:
Same DU
P Isotherms
(constant T)
V
dU = n CV dT (derived for constant
volume, but true in general)
or
g
ln(PV ) = constant
or
g
PV = constant
QED
Irreversible Processes
Examples:
arrow of time
Why?
Hot Reservoir, TH
QH
Work, W
QC
Cold Reservoir, TC
W = QH - QC
Hot Reservoir, TH
QH
Work, W
QC
Cold Reservoir, TC
K = QC / W
“Coefficient of performance”
(The larger the better.)
QH Q QH-Q
W W
QC QC
1 Qin
2
TH
P
4 3
Qout TC
e = 1 - TC/TH
The Stirling Engine
Invented by Robert Stirling in 1816.
Its operating cycle is:
1 Qin
Q 2
TH
P Q
4 3
Qout TC
dQ = dU + dW = n CV dT + P dV
= n CV dT + n R T (dV/V)
∫ dQ
f
DS = Sf - Si = T
i
(Valid for any system)
In general, the process may be too
complicated to do the integral
(particularly if irreversible process):
i 1
P 2
f
DS = n CV ln(Tf/Ti) + n R ln(Vf/Vi)
Q = n R T ln(Vf/Vi).
DSreservoir = - Q/T.
∫ dQ
T .
DSgas = n R ln(Vf/Vi).
DS = ∫ dQ
T
This implies that dQ cannot be strictly
positive. There must also be heat released
in the cycle.
Qin
TH
P
Qout TC
V
Carnot cycle: (Qin/TH) + (-Qout/TC) = 0.