August 30, 2001

Reading: Chapter Three

Homework: None

Reversible vs. Irreversible process:

Reversible --- a process during which the whole system is kept at
equilibrium. The direction of the process can be reversed by reversing the external
driving force into the opposite direction.
Irreversible --- a process during which the system is NOT kept close to
equilibrium. The direction of the process can NOT be reversed by reversing the
external driving force into the opposite direction.
An example demonstrating reversible vs. irreversible processes:
F2

F1

y1

P1,V1

V1

V2

P2,V2

y2

Isothermal
A

Heat reservoir

T=constant

Consider expansion of gas from V1 to V2 by an isothermal process.

Initially the system is at equilibrium with surroundings: P1A = F1
Finally the system is also at equilibrium with surroundings: P2A = F2
In a reversible process, the system is kept at equilibrium, force is gradually
reduced very slowly from F1 to F2 so that PA=F F (F <<F, infinitesimal
change) is maintained throughout the process. Then, the work done by the system
is
y2

y2

V2

y1

y1

V1

wrev = Fdy = PAdy = PdV

In an irreversible process, the system is NOT kept at equilibrium, so during the
y2

V2

y1

V1

process, PA F. Then wirr = Fdy PdV .

Suppose we expand the gas irreversibly from V1 (y1) to V2 (y2) by suddenly
changing F1 to F2 (F2 < F1), then the system will be off equilibrium and

spontaneously expand toward a new equilibrium where PeA = F2. Such a

spontaneous movement of a system from a nonequilibrium state to an equilibrium
state is called a spontaneous or natural process. (Examples: heat flow from high
temperature to low temperature.)
The work done by the system during this spontaneous process will be
y2

wi = Fdy = F2 ( y 2 y1 ).
y1

F
F1
F2

y1

y2

From the above figure, we see that the work done by the system during a
irreversible process is less than that during a reversible process, i.e., wirr < wrev.
Degree of Irreversibility and Entropy:
During the expansion, F PA ; otherwise, the system wont expand but shrink if
F < PA . Therefore the work done during the irreversible process is always less
y2

V2

y1

V1

than that during the reversible process, i.e., wirr = Fdy PdV . Hence, the
work done by the system has its maximum value wmax = wrev , if the process is
conducted reversibly; any irreversible process performs less work. On the other
hand, U is the same independent of process (either irreversible or reversible),
because U is a state function. Consequently, the system adsorbs the maximum
amount of heat, q rev = U + wmax , from the heat reservoir during the reversible
process. In any irreversible process, less heat is adsorbed by the system from the
reservoir, q = U + w . This indicates that in an irreversible process, despite the
system expands with an internal pressure P, it only does a work
w = Fdy = ( P P)dV < PdV = wmax ; some work (mechanical energy) has been
degraded to heat (thermal energy) during the process. Hence the system needs to
adsorb less heat from the reservoir for the same amount of change in internal
energy.
The difference between the work done during the reversible process and the
irreversible process, wmax w , characterize the amount of degradation of work to
heat caused by the irreversible nature of a process. So, the heat produced by the

degradation, i.e., q rev q = wmax w , in an irreversible process can be used as

part of the measure of the degree of irreversibility of a given process: the larger
the q rev q , the more irreversible is the process.
The effectiveness of degradation of work to heat in an irreversible process is also
influenced by the system temperature. Lets consider three irreversible processes
in which the same amount of work is degraded into heat (qdeg) at different
temperatures, as shown in the figure below:

wdeg

irreversibe
process

qdeg
T1

wdeg

irreversible
process

thermal
contact

qdeg
T1

qdeg
T2

irreversible
process
wdeg

qdeg
T2

In the first irreversible process, amount of work wdeg is degraded into qdeg entering
a heat bath of temperature T1. In the second irreversible process, amount of work
wdeg is degraded into qdeg first entering a heat bath of temperature T1 and then
flowing spontaneously into a heat bath of lower temperature T2 (T2 < T1) that is in
thermal contact with the T1 bath. In the third irreversible process, amount of work
wdeg is degraded into qdeg entering a heat bath of temperature T2 (T2 < T1). We see
that the process 3 is the sum of process 1 and 2, so the process 3 is more
irreversible than either process 1 or 2. Therefore, despite the same amount of
degradation of heat qdeg, the process 3 is more irreversible than the process 1
because 3 occurs at a lower temperature than 1. So, temperature must be taken
into account for a complete measure of irreversibility. We introduce the quantity
q deg q rev q
S irr =
=
T
T
as the complete measure of the degree of irreversibility for a given process. In the
above example, the process 3 is more irreversible than the process 1 because
q deg / T2 > q deg / T1 . S is called entropy; it will be shown that S is a state function.