Adiabatic Free-Expansion

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

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

Adiabatic Free-Expansion: Entropy Change

f process is irreversible the gas
dQrev
Sgas = =? 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
Sgas: adiabatic = Sgas: quasi = nR ln >0
V free static VA
expansion isothermal
expansion

System Entropy Change

A
VB
vacuum Ssystem = Sgas = nR ln > 0 irreversible
VA
B

adiabatic free-expansion

reservoir
Ssystem = Sgas + Sreservoir
gas +Q Q
Ssystem = + =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
Ssystem > 0 < entropy change > Ssystem = 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 SUniverse

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

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