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ENTROPY GENERATION AND LOST AVAILABLE WORK

The analysis of an open thermodynamic system requires the selection of an appropriate boundary that
can be drawn around the region of interest. The control surface or boundary can have more than one
location for mass, energy, etc. transfer. In most cases, the control surface is defined as rigid and
therefore it is impossible for the open system (or control volume) to experience work transfer by
means of forces normal to the boundary. The only possibility is work done by shear (or tangential)
forces, such as a rotating shaft that penetrates the control surface.
Open system are governed by properties related to mass, energy and entropy. The mass conservation
statement is that the mass transfer is equal to the mass change in the control volume or
(1)
The first law of thermodynamics can be written as
(2)
where the left-hand side denotes energy transfer interactions: shaft work, heat transfer and energy
transfer associated with mass transfer across the control surface. The specific enthalpy h, fluid speed
v and the height z are evaluated at the boundary location. The energy E is the systems instantaneous
energy integrated over the entire control volume. Finally, the second law of thermodynamics is
(3)
which indicates that entropy can be transferred across the control surface with the mass transfer or
that it can be generated at the boundary with heat transfer. However, the total accumulation of
entropy within the control volume (the right-hand side) maybe larger than these transfers as a result
of internally generated entropy. It is convenient to re-arrange the second law inequality as
(4)
and the quantity on the left-hand side defines the rate of entropy generation in the system [in usnits
of W/K], a quantity that is always positive and in the reversible limit equal to zero, that can be used
as a measure of a systems departure from reversibility. Thus, if systems A and B operate so that
then we state that system A is operating more irreversibly than system B.
Example of Turbine Operation: Consider the steady operation fo a steam turbine as sketched in
the figure below. Across the turbine the steam pressure drops from the input value PIn to a fixed
outlet pressure POut. As a steady flow operation the mass conservation statement reduces to
Modeling the control surface around the turbine as adiabatic without significant heat transfer permits
one to write the first and second laws of thermodynamics as

(5)
(6)
In writing the first law, Eq. (5), as shown we have neglected both the kinetic and potential energy
changes associated with the inlet and outlet streams.

The right side of the above figure, with the dashed line connecting the In starting state to the Out
final state, was drawn for the most general case in which entropy is generated; that is, the flow of
steam through the turbine is irreversible. It is customary to evaluate the performance of a given
engineering component such as a steam turbine in the reversible mode. This limiting situation is
sketched using a solid line on the h-s diagram above. Geometric reasoning alone suggests that a
reversible turbine delivers the maximum possible shaft power per mass flow rate, provided the two
pressures PIn and POut are fixed. The first and second laws in the reversible case yield
(7)
(8)
and these can be used to calculate the drop in turbine shaft power caused by irreversibility. Using
Eqs. (5) and (7) we obtain
(9)
Geometric reasoning is again helpful in recognizing that for small departures from irreversible

operation, that the enthalpy difference in Eq. (9) is proportional to the entropy increase across the
turbine; that is, to the shaded triangle in the h-s diagram. Alternatively, since
(10)
since from state Out,Rev to state Out the pressure remains constant. Thus, we can write
and
Next, we need to understand how the temperature changes with specific entropy and this can be
accomplished using a Taylor expansion of the temperature from the reversible Out,Rev state to the
actual Out state as

Remembering that the specific heat at constant pressure permits one to write

gives
(11)
or
(12)
where this average temperature lies between the two states on the POut curve. Finally, we may
conclude that the reduction in shaft power is
(13)
which indicates that the entropy generated in the system is directly proportional to the decrease in
the turbine shaft work or that the turbine power output (or the turbine efficiency) decreases with the
increasing degree of turbine irreversibility.
Example of Unsteady Filling of a Container: The thermodynamic analysis of unsteady flow
systems presents further subtleties. The figure below shows a rigid and evacuated container of
volume V surrounded by the atmosphere at state ( Po, To ). At a particular instant, the valve opens
and air from this atmosphere reservoir fills the container. The wall of the container is thin enough
so that eventually the trapped air and the atmosphere reach thermal equilibrium. We consider the
filling process to determine the total heat transfer exchanged by container air and atmosphere
through the walls of the container. For the analysis, we select the container wall as the control
surface. For the inflow duct that is in contact with the outside we position the control inflow port
upstream of the valve. This choice makes the valve as well as the irreversibility associated with it
internal to the system; that is, the valve is part of the control volume.
After the valve is opened the air pressure that occurs within the container will increase with time and
this time-dependent behaviour indicates that this situation is definitely unsteady. Conservation of

mass and the first law can be written as


(14)

(15)
where M = PV/RT and U = McV ( T - To ). The enthalpy of atmospheric air, compatible with having
chosen u = cV ( T - To ), is
(16)
We can calculate the heat transfer interaction for the filling process by integrating Eq. (15) from the
initial time ti to the final equilibrium time tf to yield

(17)
Now, since both Po and V are positive, the sign of Q is out off the container as shown in the sketch.
This result, Q = PoV makes sense if we think of the atmosphere as doing work PoV on the batch of
air pushed through the valve into the container. This batch of air eventually stores no energy since
Tfinal = Tinitial. Thus, the work PoV is completely dissipated via the filling process and it is fully
rejected back into the atmosphere as heat.
The second law of thermodynamics, Eq. (4), can now be employed to determine the degree of
irreversibility of the filling process. In accordance with the sign convention, we can write

which indicates that the entropy generation increases with the size of the container and the with the
initial pressure Po. A less obvious conclusions is that the entropy generation is proportional to the
work done by the atmosphere to drive the filling process and this can be seen by combining the
equation above with the observation that WAtm = PoV which yields
(18)
This result is similar to the arguments that lead to Eq. (13). The work done by the atmosphere, WAtm,
is lost due to the irreversibility introduced by the valve. In order to recover WAtm for use we must
eliminate the entropy generation SGen by, for example, replacing the valve with a near reversible
component such as a well-designed turbine.
Example of Hot Exhaust Stream from a Plant: Consider the starting conditions of a hot stream
flow at TH and Po where the atmospheric temperature and pressure are To and Po. A sketch shows
the arrangement as

(a) The exhaust stream is cooled to temperature To by direct thermal contact with the atmosphere.
Modeling the exhaust as an ideal gas (with constant R, cV ), we can determine the heat transfer rate
to the atmosphere and the entropy generation rate associated with this cooling process as

(b) A possible method for utilizing the hot exhaust to produce useful mechanical power is to operate
a heat engine between the stream and the atmosphere. Modeling the functioning of this scheme as
reversible we can determine the net shaft power delivered by the hot-stream - heat-engine
arrangement and the rate of heat rejection to the atmosphere as

(c) We can demonstrate that the mechanical power produced in part (b) of this example is
proportional to the rate of entropy generation determined in part (a).
.
Entropy Generation and Lost Available Work
We derive the Gouy-Stodola relation which is the relationship between irreversibility (entropy
generation) and the destruction of work in systems whose operation departs from the reversible limit.
Eliminating the heat transfer dQ/dt between Eqs. (2) and (4) and re-arranging the terms yields a
theoretical upper bound for the shaft power transfer as
(19)
where the inequality sign corresponds to the general case in which the flow system is irreversible and
the shaft power reaches its maximum value in the reversible limit,
(20)

Of engineering significance is the difference between this maximum shaft power and the actual
power transfer. Following Kestin[1] in this development we recognize this quantity as the lost
available work, WLost, and, on a unit time basis, lost available power associated with the degree of
irreversibility of the system as
(21)
where, by definition, the lost available work rate is zero when the system operates reversibly, while
in the irreversible case, the lost work rate is always a positive quantity. For example, if the shaft
work rate is also positive (out off the system), then the lost available work rate is also positive and
represents the drop in shaft work rate output attributed to system irreversibility. On the other hand,
if the actual shaft work rate is negative (into the system), then the maximum value of the shaft work
rate is algebraically greater than the actual shaft work rate, hence the lost work rate is again a
positive quantity. Thus, in this case the lost work rate represents the shaft power administered to the
system in addition to the minimum requirement
The fact that the lost work rate is always positive has nothing to do with the sign convention adopted
for the work transfer rate. Lost available work rate is a measure of the inequality sign in the second
law, a measure of the degree of thermodynamic irreversibility in the system. The work available
rate indicates that the system irreversibility is responsible for the one-way destruction of an amount
of work that would otherwise be available for use. An important relationship between the lost
available work rate and entropy generation is obtained by combining the definition Eq. (21) with
Eqs. (19) and (20) to obtain
(22)

or, using Eq. (4),


(23)
Equation (23) represents the Gouy-Stodola relation, named after the first two scientists who
recognized its importance[2]. This relation states that the lost available work rate is directly
proportional to the entropy production. For an open system, the proportionality factor is simply the
environments absolute temperature To although the exact form of the proportionality depends on
the specific features of the system of interest.
Systems Communicating with More than One Heat Reservoir
It is possible for a system to communicate thermally with more than one heat reservoir. Consider
the situation sketched in the figure below where the system of interest can exchange heat with n heat
reservoirs. For simplicity, we consider a closed system executing an integral number of cycles. The
net energy transfer interactions are Qj and W.

In a manner that is identical to the analysis that led to the Gouy-Stodola relation, Eq. (23), we begin
with the first and second law of thermodynamic statements
(24)

(25)
At this point, we arbitrarily choose to eliminate the jth heat transfer interaction between Eq. (24) and
Eq. (25) to obtain an upper bound for the net work transfer,
(26)

The maximum work transfer occurs during a sequence of reversible cycles,


(27)
Now, we subtract Eq. (24) from Eq. (27) in order to calculate the lost available work, WMax - W,

or
for j = 1, 2 ,..., n

(28)

In conclusion, lost available work is a relative quantity that depends on our choice of reference heat
reservoir. The reference heat reservoir is the one whose heat transfer interaction floats (or changes)
as the irreversibility and work output of the system changes. Subscript j in Eq. (28) can be used to
calculate not one but n quantities, all representing lost available work defined with respect to a
succession of n absolute temperatures. However, since the rate of entropy generation is the same in
all cases; that is, independent of j, Eq. (28) yields
(29)
The result, Eq. (29), is a conversion formula that relates the lost work based on temperature To to lost
work based on any other absolute temperature Tj.
Unlike lost available work, which is subject to convention, the entropy production SGen depends
solely on the degree of thermodynamic irreversibility of the system. If engineering systems and their
components are to operate such that the destruction of available work is minimized, then the design
of such systems and components must begin with the minimization of entropy generation.
Example: Consider a special case of the general n heat reservoir system where we have a heat
engine operating cyclically between two heat reservoirs; a high-temperature reservoir TH and a low
temperature reservoir TL. The engine and its thermodynamics are presented graphically in a sketch
at the end of this note. In analytical terms, we have
(30)
(31)
and, for a reversible engine,
(32)
(33)
Comparing the actual engine with the reversible engine on the basis of equal heat input; that is,

permits us to evaluate the lost available work rate as


(34)
where we have eliminated

between Eqs. (32) and (33) to obtain

Therefore, the low temperature reservoir TL assumes the role of reservoir Tj in the general analysis.
Adiabatic Systems
When the system of interest is unable to exchange heat with its environment, the lost-work entropy
generation proportionality cannot be expressed in the simple form of Eq. (23). This situation was
illustrated above using the example of a steady-flow turbine.
The concept of lost available work and entropy generation imply the comparison of the actual
(irreversible) operation of one system with the reversible operation of the same system. In this
comparison, things must change inside and/or along the boundary of the system. One of these
changes occurs in the work transfer interaction since lost available work is an obvious object of
comparison. However, the first law of thermodynamics requires a change in at least one other energy
interaction. In an adiabatic system this additional change can only be accommodated by allowing
one thermodynamic property to change (or float ) at an entry/exit port with the degree of
thermodynamic irreversibility. In the example of the turbine, we allowed the turbines outlet
temperature to change as the turbine operated less and less reversibly. Thus, the Gouy-Stodola
relation for adiabatic systems is similar to our earlier statements since the lost available work
is defined relative to boundary point j where the energy interaction is allowed to vary as the systems
irreversibility changes.
Availability (Exergy) Analysis of Steady Flow Processes
If an open system with inlet ports and outlet ports operates in steady state while exchanging heat with
the atmospheric heat reservoir at temperature To, then the maximum shaft power is
(35)
where the specific kinetic and gravitational energies of the mass flow streams into or out off the
system have been assumed to be insignificant. Expression (35) indicates that the quantity h - Tos is
an important factor in the second law analysis of steady flow processes. Following Keenan[3], we
refer to this factor as the availability function for steady flow and define it as
(36)
although it is common to see the symbol a used instead of b. It is important to bear in mind that
b is a thermodynamic property of the system as soon as the environment temperature To is specified.

You should also note the difference between the steady flow availability function, h - Tos, and the
Gibbs free energy, g = h - Ts.
For the more general case involving multiple exchanges, we can write
(37)

(38)
and, if the system is free of irreversibility,
(39)

(40)
Eliminating

in these last two equations yields

and this expression constitutes a summary of availability flow accounting along the system frontier.
The last term in Eq. (41), involving the heat flows, represents the availability of the heat transfer
interaction dQi/dt, Ti with respect to the reference thermal reservoir at temperature To ; that is, the
capacity of the heat transfer interaction to produce useful work. Thus, the term

represents the maximum work obtained when a reversible engine operates between temperatures Ti
and To with dQi/dt as the heat input. Obviously, the availability of dQo/dt, To with respect to To is
always zero and it is not listed in Eq. (41).
Although Eq. (41) might suggest an availability balance exits within the system, the existence of a
lost work term suggests exactly the opposite. In any real process, one finds an availability flow
deficit accounted for by the lost available work term. Any real system destroys availability and the
one-way destruction of availability is proportional to the entropy production.
Example of Hot Exhaust Stream from a Plant: The usefulness of the availability function b is
apparent if we re-consider this problem of a hot stream flow at TH and Po where the atmospheric
temperature and pressure are To and Po. Thus, we have one inlet at TH, Po and one outlet at To, Po in
communication with the atmosphere as a heat reservoir. Using Eq. (41), we can write that the
maximum work-producing potential of the hot-exhaust-atmosphere combination is
(42)

which is the answer that was quoted earlier. In part (a) of this situation, this work potential is
entirely destroyed by the direct contact and mixing of the stream with the atmosphere. However, in
part (b) the hot exhaust is cooled reversibly by using appropriate hardware and the availability
difference, Eq. (42), is converted into useful work.
In actual operation, any power plant attempting to perform work in this fashion would be able to
convert only a fraction of the maximum power, Eq. (42), into useful work while the losing the extra
amount to lost work. The systems departure from the reversible limit can be characterized by the
second law efficiency, defined as the ratio
(43)
where this second law efficiency lies between zero and one. This efficiency should not be confused
with other ratios (efficiencies) encountered in thermodynamics. For example, the efficiency of a heat
engine operating between two heat reservoirs (at TH and TL) is
(44)
with efficiency I denoted as the first law efficiency of the heat engine. These two efficiencies are
proportional since
(45)
where
(46)
Availability and Exergy - A Historical Perspective
The property availability, that was made popular in the U.S. by Keenan and the MIT school of
engineering thermodynamics has a number of equivalents proposed in Europe. For example, today
the term exergy, introduced by Rant[4] finds wider acceptance, particularly since it can be adopted
without translation in other languages. Much earlier, the thermodynamic literature was acquainted
with such descriptive terms as Die grsste Nutzarbeit (or maximum useful work, Clausius[5]), Die
technische Arbeitsfhigkeit (or capability of performing work, Bosnjacovi[6]), and Energie
Utilisable (or useful energy, Darrieus[7]). The last term is perhaps responsible, in part, for todays
fashionable reference to an energy crisis or to energy conservation, when, in effect, they really
mean available work rather than energy. Kestins term lost available work is most descriptive
and least enigmatic.
Exergy, denoted by the symbol ex, like availability b, is a thermodynamic property of the system
(47)
where ho and so are properties evaluated at the temperature and pressure of the environmental dead
state at To, Po. The symbol ex used here should not be confused with the total specific energy
According to definition Eq. (47), the exergy of the outflowing stream in the example above is zero.

Comparing definitions Eq. (47) and Eq. (36), we can see that availability is numerically identical to
exergy in cases where ho and so are taken as zero.
Finally, it should be noted that the focus herein is on the evaluation and minimization of entropy
generation in engineering systems. The concept of availability and its equivalents are used only
sporadically since the minimization of entropy generation is equivalent to the minimization of
availability destruction [see the Gouy-Stodola relation, Eq. (23)].
Steady Flow versus Non-Flow Availability and Exergy
The availability accounting procedure and the exergy property discussed so far are designed to shed
light on the maximum work-producing potential of systems in steady flow. The exergy ex of a
stream, Eq. (47), is the maximum work extracted as the stream reaches the dead state.
In many applications it is important to determine the maximum work content not of a stream but of
a closed system in communication with the environment. For example, we may want to know the
maximum work we can store as compressed air in a bottle. To determine the maximum work we
imagine a reversible process where, as sketched below, the closed system reaches the dead state
(To,Po) by first undergoing a reversible and adiabatic expansion and then a reversible and isothermal
expansion (for clarity in the sketch it has been assumed that T > To and P > Po). For the entire
process we have
(48)
(49)

Sketch of the reversible process for calculating the exergy of a closed system
in thermal and mechanical (via piston) communication with the atmosphere.
This arises from the definitions h = u + Pv and g = u + Pv - Ts = h - Ts which means that exergy
is ex = h - Tos - [ ho - Toso ] = b - go where go is the specific Gibbs free energy in the dead state.

The maximum work delivered by the system, WMax, is only partly available for use as one fraction,
Po( Vo - V ) is spent in order to displace the atmosphere. The remaining fraction is the exergy of the
closed (non-flow) system[8]
(50)
It is sometimes convenient to recognize the property
(51)
as the non-flow availability[4]. The non-flow exergy is the change in non-flow availability between
the initial state and the dead state; that is,
(52)
Characteristic Features of Irreversible Systems and Processes
Improving the thermodynamic performance of an engineering system requires the proper
identification of those features (components) most guilty of entropy production. There exist a
number of basic features that are extremely common in real applications and we shall consider a few
of these features in an attempt to provide insight into irreversible operation.
Heat Transfer Across a Non-Zero Temperature Difference
Consider the sketch below in which two systems (or bodies) of different temperature TH and TL
experience a finite heat transfer interaction, Q. An important observation is that the two systems do
not communicate directly because if they did, then they would have a common boundary and the
temperature TH would eventually equal the temperature TL. Sandwiched between these two systems
is a third system usually referred to as the temperature gap. The heat transfer Q enters and leaves
the sandwiched system undiminshed.
If we apply the second law of thermodynamics to this temperature gap, then the entropy generation
in this space is
(53)
and this entropy generation is positive so long as the temperature difference exists since TH > TL.
The irreversibility associated with this feature is proportional to the temperature difference and the
heat transfer that crosses the gap and the available work lost as a result of this irreversibility is
proportional to SGen. For example, using the availability formulation, Eq. (41), the lost work equals
the availability of the heat transfer interaction QH, TH with respect to TL
(54)
The right-hand sketches in the figure below indicates how a heat transfer from TH to TL is
thermodynamically equivalent to a reversible engine that operates between these two temperatures
and dissipates its entire work output into a brake, rejecting heat to either temperature reservoir.
Thus, minimizing the heat transfer irreversibility makes it possible to harness this available work,

in power systems and in refrigeration systems.

Destruction of available work by heat transfer across a non-zero temperature difference.


Flow with Friction
An equally common feature is the presence of fluid friction in the pipes of various engineering
installations. Consider, for example, the steady and adiabatic flow of a pure substance through a
short segment of pipe. The inlet conditions are TIn, PIn while the outlet pressure is lower than the
pressure at the inlet; that is, POut = PIn - P.
The first and second laws of thermodynamics indicate that
and

(55a,b)

Realizing that the enthalpy change for a pure substance is given by dh = Tds + vdP = 0 permits us
to write the entropy change as ds = - ( v/T )dP so that we can write the entropy generation rate as
(56)
and, since both v and T are positive, the entropy generation rate is positive as soon as the pressure
drop takes place between the inlet and outlet with PIn > POut. This can also be seen easily in the
limits of pure substance behaviour, namely, an ideal gas flow (with gas constant R and specific heat
cV) where
where

(57)

and an incompressible fluid flow (with specific heat c and density )


where

(58)

The relationship between entropy generation and lost available work is easy to see in the case of fluid
friction since, obviously, we must invest useful work to push the fluid through the pipe. The lost
available power can be calculated based on availability flow arguments, Eq. (42), as
(59)
and this shows that the stream availability decreases along the pipe with the decrease being
proportional to the pressure drop P and the mass flow rate.
Further Examples of Irreversibility in Processes
In addition to heat transfer, fluid friction and mixing, there are other features that can be viewed as
irreversible such as filling and discharge (associated with the operation of reciprocating machinery),
compression/expansion and combustion.
Discharge processes occur in much the same manner as the filling process (of a container) discussed
earlier, their irreversibility being associated with the pressure drop across the outlet. Irreversibility
of a compressor may be due in part to features such as filling and discharge however the compressor
irreversibility is also due to compressing the working fluid in a manner that departs from the quasistatic limit required for reversible compression. To be more specific, when a gas is compressed
rapidly it is set in motion internally. Viscous and inertial effects dictate how fluid currents (eddies)
form and decay locally in the compressor chamber. The gas-cylinder-wall interaction is also
important. Eventually, the relative kinetic energy of different fluid packets is dissipated locally
through friction, the overall result being the generation of entropy. The irreversibility of combustion
processes is an important subject but beyond our current introduction.
References
[1] J. Kestin, Availability: The Concept and Associated Terminology, Energy Int. J., 5, 679 (1980).
[2] M. Gouy, Sur lEnergie Utilisable, J. Phys., 8, 501 (1889); A. Stodola, Steam and Gas
Turbines, McGraw-Hill, New York (1910).
[3] J.H. Keenan, Thermodynamics, MIT Pr., Cambridge, Mass. (1941), Chap. 18.
[4] Z. Rant, Exergie ein neues Wort fr technische Arbeitsfhigkeit, Forsch. Ing. wes., 22, 36
(1956).
[5] R. Clausius, Die Mechanische Wrmetheorie, Braunschweig (1887).
[6] F. Bosnjacovi, Technische Thermodynamik, vol. 1, Steinkopf, Dresden & Leipzig (1953).
[7] G. Darrieus, Levolution des Centrales Thermiques et al Notion dEnergie Utilisable, Sci.
Industrie, 15, 206 (1931).
[8] R.W. Haywood, Equilibrium Thermodynamics, Wiley, New York (1980).

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