Lecture 7

Maximum work

7.1 Overview
In a previous lecture, we examined several examples where we estimated the maximum amount of
work that could be obtained from a system. These calculations were ad hoc, meaning that we had
to examine each system individually, on a case by case basis. There is also the worry that perhaps
we were not clever enough to think of a better way of extracting the work. In this lecture, we will
develop a general method of computing the maximum amount of work that can be obtained from a
process. Along the way, we will introduce the concepts of availability and exergy.
The maximum work that can be produced by a system depends on the constraints that we place
on the system and on its surroundings. In the following section, we consider a closed system. Then,
we generalize this result to open systems.

7.2 Closed system

We first consider a closed system, which can exchange heat and work with its surroundings but does
not exchange material. It initially has a temperature T and a pressure p. We assume that the sur-
rounding environment has a temperature T0 and a pressure p0 , and that it is sufficiently large that its
properties remain constant.
To calculate the total amount of work that can be generated from this system, we first consider
the amount of work Wtherm that can be obtained from allowing the system to cool (or heat) from its
initial temperature T to the temperature of surrounding environment T0 . Then we consider the work
Wexp which can be obtained from the expansion (or contraction) of the system.
If the temperature of the system is lower than the environment, then an amount of heat Q will
naturally flow into the system. The amount of this heat is related to the entropy of the system entropy
by
Q T dS (7.1)

We can place a Carnot engine to extract work Wtherm from this heat flow. In this case, the total heat
drawn from the environment is Qenv = Wtherm + Q. The resulting work is then
   
T T
Wtherm = 1 Qenv = 1 (Wtherm + Q)
T0 T0
 
T0
= 1 Q
T
 
T0
1 T dS
T
(T0 T )dS

38
 If the temperature of the system is higher than the environment, then heat will naturally flow out
of the system (i.e., Q < 0). This is related to the entropy of the system entropy by Eq. (7.1). We can
again place a Carnot engine between the system and the surroundings to extract work, however, now
the system will be the heat source and the environment will be the heat sink. The work is then
 
T0
Wtherm = 1 Q
T
 
T0
1 T dS
T
(T0 T )dS,

which is the same as the previous expression.
In addition to the thermal work, the system may also expand (or contract) due to a difference in
the pressure. From this change in volume, we can extract work Wexp

Wexp (p p0 )dV (7.2)

The total work W that can be obtain from the system is the combination of the work from heat
transfer and expansion:

W = Wtherm + Wexp
= (T0 T )dS + (p p0 )dV

= T0 dS p0 dV T dS + pdV

= T0 dS p0 dV dU

We can integrate this expression between two states to obtain:

W = U + T0 S p0 V (7.3)

Therefore the maximum amount of work that we can obtain from the transformation of a closed
system is given above. The maximum amount of work that we can extract from the system is:

W = (U U0 ) + T0 (S S0 ) p0 (V V0 ) (7.4)

where U0 , S0 , and V0 are internal energy, entropy, and volume, respectively, the of the system at the
temperature and pressure of the environment. When the system is in equilibrium with its surround-
ings, then we are unable to extract any work from it.
This expression motivates the definition of the availability

= U U0 + p0 (V V0 ) T0 (S S0 ) (7.5)

for a closed system. The maximum work that can be extracted from a closed system is equal to its
availability. The maximum work that can be obtained from a system that transforms between two
states is given by the difference in the availability.

7.3 Open systems

Lets now consider a system where material from the surroundings can leak into the system or material
in the system can leak out into the environment.

39
 The entropy change of the environment is
1 p0 X 0,
dSenv = dUenv + dVenv dNenv,
T0 T0
T0

1 p0 X 0,
= (dU + W ) dV + dN
T0 T0
T0

where we have used the fact that dUenv + dU + W = 0 from the conservation of energy.

For our analysis, we will consider both the system and its environment together. For this composite
system, which we refer to as the universe, the total energy and volume are constant; the combined
first and second law of thermodynamics then requires that the entropy Suniv of the universe obeys

dSuniv = dS + dSenv 0
X 0,
1 p0
dS (dU + W ) dV + dN 0
T0 T0
T0

where S is the entropy of the system, and Senv is the entropy of the environment (surroundings).

X
W dU + T0 dS p0 dV + 0, dN

7.4 Flowing systems

Now we consider a system with boundaries that are open, with several streams which may either be
entering or exiting the system. Stream k will have a pressure pk , a temperature Tk , and a corresponding
molar volume Vk . Let us focus on a small interval of time dt, during which dNk moles of stream k
enter the system (or leave if dNk < 0).
The flow of material into the system actually performs work on the system. The work performed
by stream k, which displaces a volume Vk dNk into the system, is pk Vk dNk . Summing this over all the
streams entering or exiting the system gives the flow work Wflow :
X
Wflow = pk (Vk dNk ). (7.6)
k

Flow of material into the system from stream k will carry with it an amount of entropy Sk dNk ,
where Sk is the molar entropy of the stream. Performing an entropy balance over the system, we can
write the second law of thermodynamics as
Q X
dS + Sk dNk , (7.7)
T k

where the first term on the right side of the equation is the entropy change due to heat transfer to the
system, and the second term is the entropy change due to transport of entropy into or out of the system
with the material from the various streams. The work that can be extracted from heat transfer to and
from the system can be determined as was done previously for the closed system:
!
X
Wtherm (T0 T ) dS Sk dNk . (7.8)

k

The work that can be obtained from expansion of the system is given by

Wexp = (p p0 )dV,

40
which is the same as for the closed system.
Finally, we need to determine the work W 0 that is performed directly by the system. We can
do this by performing an energy balance over the system. The influx of material from stream k will
carry with it internal energy Uk dNk , where Uk is the molar internal energy of the stream. From an
energy balance over the system, we find
X
dU = Q W 0 pdV + Uk dNk

k
X
0
W = dU + Q pdV + Uk dNk

k
" #
X X
dU + T dS Sk dNk pdV + Uk dNk .

k k

We can now determine the total amount of work W that we can extract by summing the various
types of work that are generated

W = W 0 + Wtherm + Wexp + Wflow

X X
= dU + T [dS Sk dNk ] pdV + Uk dNk

k k
X X
+ (T0 T )[dS Sk dNk ] + (p p0 )dV + pk Vk dNk

k k
X
= d[U T0 S + p0 V ] + (Hk T0 Sk )dNk

k

The first term is the same as for the closed system and represents the work that can be extracted from
simply flowing heat to or from the system and from expansion of the system. The second term is
different, and represents the work that can be extracted from the net inflow of material to the system.
Dividing by the interval of time dt, we arrive at an expression for the rate at which work can be
generated:
d X
W = [U T0 S + p0 V ] + Nk (Hk T0 Sk ) (7.9)
dt
k

7.5 Exergy
For a steady state process, then there is no accumulation in the system, so the time derivatives of U ,

S, and V vanish, and the work is

X
W = Nk [Hk T0 Sk ]. (7.10)
k

From this analysis, we are motivated to define a quantity which we refer to as exergy B

B = H T0 S. (7.11)

This only depends on the thermodynamic state of the system and the temperature and pressure of its
surroundings.
The work from a steady state system is then
X
W = Nk Bk , (7.12)
k

41
which is just the net difference in the exergy of the input and output streams. If the exergy change is
negative, the work can be extracted from the system. If it is positive, the work needs to be input to the
system.
For a general time varying system, we have:
X
W = + Nk Bk . (7.13)
t k

7.6 Conclusions
In this lecture, we have develop a general method to determine the maximum of work we can extract
from a system, whether it is a closed system, an open system, or a system with flowing inlet and outlet
streams.
Availability represents the amount of work that we can extract from a closed system. Exergy rep-
resents the amount of work we can extract from a stream. Note that exergy is not a conserved quantity.
In a general irreversible process, the exergy of a stream (or availability of a closed system) will be
lost. Only in a process with reversible transformations will exergy (or availability) be conserved.

42