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Adiabatic Free-Expansion

A
thermal energy transfer to gas?
vacuum
Q = 0 <— adiabatic
B work done by gas?
W = 0 <— free

1st Law: ΔU = Q − W = 0
3 3
eqn of state: U = nRT so ΔU = nRΔT
2 2
and TA = TB

Adiabatic Free-Expansion: Entropy Change


f process is irreversible — the gas
dQrev
ΔSgas = ∫ =? will not spontaneously occupy one
i
T half of container
—> entropy change must be
positive

to calculate change in entropy,


P A
connect A and B by a reversible,
quasi-static isothermal “model”
process
B
VB
ΔSgas: adiabatic = ΔSgas: quasi− = nR ln >0
V free− static VA
expansion isothermal
expansion

System Entropy Change


A
VB
vacuum ΔSsystem = ΔSgas = nR ln > 0 irreversible
VA
B

adiabatic free-expansion

reservoir
ΔSsystem = ΔSgas + ΔSreservoir
gas +Q −Q
ΔSsystem = + =0
Q T T
VA VB reversible

quasi-static isothermal expansion


Work Done by Gas
System I
reservoir System II
A
vacuum
gas
Q
B

VA VB

irreversible adiabatic free-


reversible quasi-static isothermal expansion
expansion
ΔSsystem > 0 <— entropy change —> ΔSsystem = 0
VB
Wa. f .e = 0 <— work done —> Wq.s.i.e. = nRT ln
VA
Note that energy of each system did
not change, yet in one case the gas
did work while in the other it did not

Availability of Energy, or “Lost Work”


• work could have been done by System I
—> the quality of the energy was lowered by
free-expansion/irreversible process

• in an irreversible process energy equal to TC ΔSUniverse


becomes unavailable to do work, where TC is the
temperature of the coldest available reservoir
—> this is known as “lost work”
Wlost = TC ΔSUniverse

Entropy as a Measure of Quality


• example – heat engine:
—> extracts thermal energy QH at high temperature
—> exhausts thermal energy QL at low temperature

this energy is of lower quality


because we need an even lower
temperature reservoir to convert
some of it to work
• given an amount of energy, it is high quality & low
entropy if it is localized, coherent, or at a high temp