The Use of the Second Law of

Thermodynamics inin Process

Design
Sarna
D. A. Sama point.
Professor of Chemical Engineering,
University of Massachusetts Lowell, fuel, equipment,
Lowell, MA 01854
importance of using the
The importance the second
second law of thermodynamics
thermodynamics in in the
the design
design of ofheat
heat
exchangers,
exchangers, heat heat exchanger
exchanger networks,
networks, and and processes
processes in in general,
general, isis discussed.
discussed. TheThe
optimal
optimal AT ll. T at a refrigerated
refrigerated heat
heat exchanger
exchanger is considered
considered from from a second
second law view-
point. It is shown
shown that the use of of minimum
minimum totaltotal annualized
annualized cost cost as the single
single optimiz-
ing factor
factor is is unsatisfactory.
unsatisfactory. Total annualized
annualized costs are based based on predicted
predicted costs of of
equipment, and and capital, which
which are uncertain at at best. Instead
Instead of a singular
singular or or
"global optimum"
"global optimum" AT, ll.T, there is a range
range of optimal AT.? over
optimalll.Ts over which
which the total
total annu-
alized
alized cost
cost is essentially
essentially the same, but but within
within which
which the distribution
distribution between
between costcost of
of
capital
capital and
and cost
cost of energy
energy isis significantly
significantly different. In In selecting
selecting a design
design AT,
ll. T, this
distribution
distribution of costs
costs should
should also
also be considered.
considered. The possibility
possibility of of only
only one singular,
singular,
or
or global
global optimum, solution
solution for complex
complex processes
processes is is also
also considered
considered from
from a philo-
sophical
sophical viewpoint,
viewpoint, andand is again
again rejected. The existence
existence and and identification
identification of design
design
decisions
decisions which
which unnecessarily
unnecessarily waste thermodynamic
thermodynamic availability (physical exergy)
availability (physical exergy)
are discussed
discussed and and identified
identified as "second
' 'second law errors.''
errors. " Elimination
Elimination of a second
second law
error from
from a design
design guarantees an an improved
improved design. An An optimal
optimal design, which
which may
be
be any
anyoneone of of aa numerous
numerous set set of
of optimal
optimal designs,
designs, will
will result
result when
when all
all second
second law law
errors
errors are
are eliminated.
eliminated. A A design
design procedure
procedure to to develop
develop optimal
optimal process
process designs, using
designs, using
such
such thermodynamic
thermodynamic insights,
insights, is proposed.
is proposed.

Introduction Availability, BB == H
H T0 S, isisaameasure
- ToS, measure of ofdeparture
departure fromfrom
the ambient. In In Fig. 1,
1, the temperature of of the hot stream ap-
The second law of of thermodynamics, broadly stated, is is that
proaches the ambient temperature, To; T; therefore, its availability
of rules which governs all changes occurring in
series of in Nature.
It applies to all processes-chemical,
processeschemical, biological, informational,
informational, goes down. The temperature of of the cold stream moves furtherfurther
etc.as well as to
etc.-as to heat/work
heat/work transformations.
transformations. One
One would
would ex-
ex- away from To; T; therefore, its
its availability goes up. Thus, it it is
is
pect, therefore, that the second law would be used extensively B, is
clear that availability, B, is transferred
transferred from the hot stream to to
in the design ofof processes. Unfortunately, this is is not the case. the cold stream.
The objective of of this paper is to
to encourage increased use of of Availability isis consumed whenever heat transfer occurs
the second law of of thermodynamics in in the design of
of processes. difference greater than infinitesimal. Since,
across a temperature difference
The paper is is presented inin two parts: 1)
1) use of
of the second law transfer path, there is a finite tempera-
at all points along the heat transfer
in the design ofof heat exchangers; 2) 2) optimization ofof designs. difference between the hot and cold streams, some .avail-
ture difference avail-
to be consumed in
ability has to in the process.
The consumed availability, which can easily be be calculated
Use of
of the Second Law in
in the
the Design of
of Heat Ex- quantitatively, has traditionally been called "lost" work. This
changers is most unfortunate. The availability was not lost. It It was ex-ex-
In general, energy crosses system or
or process boundaries in
in pended
pended to to allow the heat transfer process to to occur inin aa finite
finite
two
two forms:
forms: finite cost. Both of
time, and in a heat exchanger offinite of these results
far more important than the
are far the quantity of of availability ex- ex-
1 work:
work: energy
energy which
which can,
can, in
in principle,
principle, be
be quantitatively
quantitatively
converted to the lifting of
of aa weight; pended.
2 heat: energy, transferred due to to aa temperature driving- A more detailed discussion of of availability changes in in heat
force, which can never be totally converted to work.
work. exchangers, and their significance can be found in SarnaSama ((1992).
1992).

The second law can be be used toto quantify the

the thermodynamic
thermodynamic
equivalence ofof heat to
to work, i.e., exergy or
or availability. How-
ever, the real significance of the second law is often directional,
Expended B
(Sama, 1992, 1993,
not quantitative, (Sarna, 1993, 1995). Thus, even without
quantitative calculations, the second law can give specific in-
to the design of
sights to of aa process, or
or to
to the improvement of of an
design.
existing design. T
The Heat Exchange Process. We We will consider the the ex-
ex-
change of
of heat between two streams asas shown in in Fig. 1. Heat,
Fig. 1. Heat,
Q, is
is transferred from aa hot stream to
to aa cold stream, both of of
which are above the ambient temperature, T To.0.
To - - - - - - - - - - - - - - - - - - - - -

Contributed by the Advanced Energy Systems

Systems Division for publication in
in the
the
JOURNAL OFOF ENERGY RESOURCES TECHNOLOGY. Manuscript received by the AES AES H
Division, April 26,
26, 1994;
1994; revised manuscript received March 25,
25, 1995.
1995. Technical
Technical
Editor:
Editor: A.A. O.
O. Arnas.
Arnas. Fig. 11 Heat
Fig. Heat transfer above ambient
ambient

Journal
Journal of
of Energy
Energy Resources
Resources Technology
Technology SEPTEMBER 1995,
SEPTEMBER 1995, Vol.
Vol. 117
1 1 7I/ 1179
79

Copyright 1995 by ASME

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 Trade-Off
Trade-Off Between Costs of Availability and Capital in Parameters Used

Heat Exchangers. A refrigeration

refrigeration heat exchanger provides 6 0 0 0 . . , . - - - - -_ _ _ _ _ _ _ _- , kr ($6/10 6 Btu)
$5,687/10' J, ($6/10'
k f = $5.687/10' Btu)
F w =1.67
= 1.67
trade-off between the cost
an excellent opportunity to study the trade-off w

of availability expended in a heat exchanger and the capital cost 8. 5000

T""
_ Total
Total Ann.
Ann. Cost
Cost
F = 3.21
Fbb = 3.21
29.52x106s sedyear,
II = 29.52x10
Hy sec/year,
of the exchanger (Sama, 1983). Suppose, for example, that we ~ 4000 - Ann. Cap. Cost (8200
(8200 hrslyear)
hrs/year)
refrigeration to the condenser of a distilla-
have a need to supply refrigeration ~ 3000 Ann. Fuel
-a- Ann. Fuel Cost
Cost T Q = 313.7.
To 313.71 K, (564.61'
(564.67 R)
R)
tion column that returns condensate as "reflux" to the column .., 10 6
Q = 29,308 kW, (100 x 10'
refrigeration temperature must be
at a fixed temperature. The refrigeration ~ 2000 Opt. = 5.565' C, (10.02' F) Btu/hr)
Bluthr)

less than this condensing temperature. What should the tempera- g: \:i T = 280.37
28037 K,
K,(( 504.67"
504.67 R)
~ 1000 $86.Il/m 2 , ($Sift')
k e = $S6.llIm',
k, ($8/fl2)
ture difference
difference be?
refrigeration temperature decreases, the temperature
As the refrigeration
00
~~;>:!:~~:::::=~:::::=;::;::;:::::d
10 15 20 25
F, = 2.2
F,=2.2
P, = 3 years
Pt =3years
difference between the refrigerant
difference refrigerant and the distillation column AT, 0 F U=567.8W/m
20
U = 567.8 W/ra 2 C,
C,
difference results in
reflux increases. This larger temperature difference (100 Btufhr ft2 oF)
Btu/hr ft2 F)
a smaller and less expensive condenser. However, the power
Fig. 2 Annualized cost versus AT,
A T , propylene refrigeration heat ex-
required to provide a unit of refrigeration
reqnired refrigeration increases as the re- (Sama, 1983)
changer (Sarna,
frigeration temperature decreases. This power increase results
frigeration
in increased fuel costs to generate the additional steam required
to drive the refrigeration
refrigeration compressor. We have a typical "opti-
mization' ' problem. At what /:::,.T,
mization" AT, between the distillation reflux
reflux process, resulting in enhanced fuel savings. Equations (1) and
and the refrigerant, will the total of the annual fuel cost and the (3) do not apply in such cases (Sama, 1983). More information information
annualized cost of capital for the condenser be a minimum? on the application of these equations may be found in that
From second law considerations, the annual cost of fuel due article.
availability expended
to availability expended at the condenser was found to be Equations (1) to (3) (3 ) were used to determine the optimum /:::"T AT
C
(Sama, 1983) refrigeration at 77.22
with propylene refrigeration .22C C (45F). The refrigeration
refrigeration
duty was 29,308 kW (l00 (100 XX 10 6 Btu/hr). The results are shown
(/fc / F,F 4 i^T 0 gAT , )/r 2
Annual Fuel Cost = (kfF",FbHyToQ/:::"T)/T2 (1) in Fig. 2, as a plot of costs versus A r , and in Table l.
/:::"T, 1. For the
values of the parameters chosen, the economic optimum AT /:::"T is
The annualized capital cost of the heat exchanger (assuming
(10.02F).
5.565C (l0.02F).
that the exchanger is large, and, therefore, directly proportional
to its area) is Consideration of these results leads to several interesting con-
clusions. The first is that at the "exact" economic optimum /:::"T Ar
Annualized Capital Cost = (keF/Q)/(P,U/:::"T)
(keFiQ)/(P,UAT) (2)
(2) (10.02F), the annual
of 5.565C (1O.02F), annual cost offuel of fuel for availability
for the availability
expended at the exchanger ($585,000 per yr) is exactly
expended exactly equal
The total annual cost of fuel and capital is the sum of the annualized capital
to the annualized capital cost ofof the exchanger. This is rather
differential of this sum, with respect
preceding equations. The differential confirmation of the direct trade-off
dramatic confirmation trade-off between the cost
to AT,
/:::"T, is set equal to zero and is used to determine the economic of fuel due to availability consumed and the cost of capital.
optimum temperature difference. This optimum temperature dif- (Note that this exact correspondence is not to be expected at
ference, ATo,/:::"To, is all heat exchangers.)
ATo = T 4{keF,)l(kfFwFbHyTBP,U) (3) The second important conclusion is that the total annual cost
optimum /:::,.
in the vicinity of the optimum AT T is quite fiat.flat. There is little
Equation (3) shows that the economic optimum AT"is /:::"T is pro- economic penalty incurred by designing at a AT /:::"T a "bit"
"bit" more,
portional to the temperature level at which heat exchange oc- ' 'bit'' less, than the economic optimum.
or a "bit"
refrigeration systems. The
curs. This is well understood for refrigeration An equally important, but less obvious, observation is that
"value" of refrigeration
"value" refrigeration increases as the temperature decreases; the graphs of costs shown in Fig. 2 are exact solutions to equa-
hence, smaller ATs refrigeration temperature
/:::,.Ts are used as the refrigeration tions which are themselves not exact. These equations were
goes down. What is not anticipated is that in above-ambient derived using reasonable, but simplifying, approximations. In
systems, such as Rankine cycles, larger A r s should be used at
/:::"Ts addition, values of the parameters used with these equations are
higher temperatures, even though the' the ' 'value"
'value'' of heat increases also inexact. Some parameters are predictions
predictions of of future prices.
future prices.
with increasing temperature. The cost of fuel and the cost of capital rise and fall regularly.
Care should be taken in the use of Eqs. (1) and (3). Avail- The cost of a heat exchanger is also not a precise and immutable
ability is not a conserved quantity. In some situations, availabil- effects of inflation, the cost of a heat
number. In addition to the effects
ity saved at a heat exchanger does not result in a fuel saving. exchanger depends on the economic status of the manufacturer. manufacturer.
In other situations, availability saved in a heat exchanger is Does the firm have more work than it can handle? Does it have
accompanied by further availability savings elsewhere in the employees who have little to do, but whom it does not want to

Nomenclature
Nomenclature
B == availability (physical exergy), Hv = operating
Hy operating time per year, s/yr, hi
year, s/yr, h/ Q == heat, or refrigeration duty per unit
J (BTU) yr) time, kW (BTU/hr)
C = degrees
degrees Celsius
Celsius ke = ; purchase cost per unit of heat ex- S = entropy, JrK
J/K (BTU/OR)
(BTU/R)
F:= degrees Fahrenheit
of changer area, $/m22 ($/ft($/ft2)) T == absolute temperature, K K (R)
(R)
Fb = units of fuel fired in plant kf =cost
costofofunit fuel,$IJ
unitofoffuel, $/J($IBTU)
($/BTU) refrigera-
To = absolute temperature of refrigera-
shaft work
boiler per unit of shaft k W :=: kilowatts
kW kilowatts tion system condenser, or of am-
produced mCp =- flow
flowheat capacity,MWrC
heatcapacity, MW/C(BTU/(BTU/ bient
:
F, = installation cost factor
F/ factor hr OF)
F) A r = temperature difference, approach,
/:::"T
F",
Fw, == units of shaft work required
required nc--= no. of cold streams
nc (F)
C ("F)
refrigeration system to de-
by refrigeration n -= no. of hot streams
nil
h ATo = optimum temperature difference
/:::,.To difference
liver unit of availability P,-= allowable payout time in years
P, coefficient,
U = overall heat transfer coefficient,
H = enthalpy, J (BTU) W/m22 c
C (BTU/hr fe ft2 OF)
F)
HEN(S) = heat exchanger network(s)

180 I/ Vol.
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 fire? According to to the
the heat exchanger specialist at at the
the Stone Table 2 Costs of fuel and capital at 7'F
7F versus 14'F AT" (~4'C
14F AT (~4C versus
~8'C)
~8C)
and Webster Engineering Corporation (Comley, 1978), the dif-
ference between the the high and
and low
low bids forfor the
the identical heat DeltaT
Delta T" Cost Fuel 8AFuel
Fuel CostCapital
Cost Capital Total
Capital 8ACapital TotalCost
Cost 8ATotal
Total %
%
exchanger was was generally a factor of 2.5 2.5 toto 1.
1. Also, who
who cancan :E
IS. :J;
1C $1000
$1.000 From
From 14 F iL.QQQ
14 OF $1.000 From
From 14
14OFF ll.QQQ
$1.000 From
From14 F ~
14'F Dev.
7 3.889 409
409 -409
-409 838
838 +419'
+419' 1,247
1,247 +\0
+10 0.81
0.81
specify exactly what the installation cost factor is? Why should
specify 14
14 7.778
7.778 818
818 ... 419
419 ... 1,237
1,237
the installation cost for
for the identical
identical heat exchanger depend on on
its purchase price, which could vary by by a factor of 2.57
2.5?
Clearly, it is
is impossible to to predict the
the costs asas precisely as
as
is shown in in Fig. 2.
2. These cost curves should be be envisioned as
as 7F than atat 14F, butbut the capital cost of the exchanger is is twice
fuzzy bands, notnot asas sharp lines. We
We cannot logically conclude as much. .
AT of exactly S.565C
that a t:.T 5.565C (1O.02F)
(10.02F) isis the singular optimum If
If the
the cost parameters chosen are are reasonably accurate, the the
AT at
t:.T at which the the total aimualized
annualized cost is is unequivocally the
the cost of fuel decreases by by about $400,000 per yr at a t:.T
yr at AT of 7F
minimum. In In our
our attempts to to be
be as
as cost-efficient
cost-efficient asas possible, (~4C), compared with 14F (~8C). This decrease is is offset
offset
we must remember not not to
to go
go overboard. We We cannot conclude, by a commensurate increase in cost of capital of about $400,000
in spite of our attempts at at optimization, that there is a "global"
"global" yr. Thus, if reducing fuel consumption is
per yr. is more important
optimum t:.TAT atat aa heat
heat exchanger.
exchanger. than reducing capital costs, the design t:.T AT should be about 7F
Indeed, wewe must conclude that there is is no
no such thing asas a ((~4C).
~4C).
global optimum t:.T.AT. Instead, there is is a range of values of t:.T,
AT, On the other hand, if capital for for construction is is in
in short sup-
all of which give minimal total annual costs. ply, the
the design should be be at A r of about 14F (~8C). At
at a t:.T At
the assumed payout time of 3 yr, yr, there is is a saving of about
The Design Decision for for tl.T
AT at at aa Refrigeration Heat Ex- $1,200,000 in initial construction costs, with no increase in total
changer. Now Now that it is is understood that there is is no
no single annualized costs.
optimum t:.TAT for the foregoing refrigeration
refrigeration heat exchanger, the the Thus, there is is a significant
significant difference
difference between the the designs
question remains: How should the the design t:.T
A T bebe determined?
determined? within this t:.T
AT range, and and there is is an opportunity to
an opportunity to make a
is my
It is my firm
firm belief
belief that design decisions should not not be
be made significant design decision. This opportunity should not
significant not bebe
by blindly plugging numbers (with or or without a computer) into wasted!
a set of equations, as as in
in the foregoing. Decisions should always The preference would be be to
to design, depending on on the
the given
after careful
be made, after careful consideration of the predictions of such circumstances, at at a t:.T ~4C), or
A r of either 7F ((~4C), or 14F (~8C).
(~8C).
equations, by the engineer. In this case, the following procedure Some might preferprefer to to design atat exactly 1O.02F
10.02F (S.SS6C).
(5.556C).
is recommended. the total annualized costs are
Since the are essentially thethe same, none
First, the
the annualized costs should be be tabulated asas a function
function of these choices would be be "wrong." However, these are are sig-
of t:.T,
AT, asas is
is shown inin Table 1, from Sarna
Sama (1983). One should nificantly different
nificantly different design decisions, since the the distribution be-
be-
then decide, using best personal judgments, the t:.T AT range over tween fuel cost and capital cost is is quite different.
different.
which there is is no
no meaningful
meaningful cost penalty. At At the
the calculated It would bebe a mistake, however, to to design at at a substantially
optimum t:.TATof 10F (close enough to 1O.02F),
of lOoF 10.02F), the total annu- higher oror lower t:.T.
A r . From Table 1, 1, it is
is seen that at at a t:.T
AT ofof
alized cost is is $1,171,000. At At a t:.T
AT of 7F, the total annualized 25F (~14C), there is is an
an increase in in total annual costs of of
is only 6.5
cost is 6.5 percent greater. At At a t:.T
AT of 14F, thethe cost is about $500,000 per yr, or or 45 percent. At AT of 4F (~2C),
At a t:.T (~2C),
only 5.6 percent greater. These differences
differences are certainly far less there are similar increases. These increased costs are significant significant
than the overall uncertainty in in the assumptions and parameters and must be be avoided. Thus, for for this heat exchanger, a t:.T AT ofof
used inin arriving at the calculated optimum. It cannot be claimed 25F (14C) is is excessively large, while one of only 4F (2C)
10.02F is
that 1O.02F is the
the optimum
optimum design. Instead, one one can
can safely
safely is excessively small.
conclude that any any t:.T
AT between about 7F 7F (~4C), and and 14F
14F
(~8C), is is an
an optimal
optimal design t:.T
AT from a total annualized cost Second Law Errors in in Heat
Heat Transfer.
Transfer. As As aa general
general state-
state-
viewpoint. ment, it may be be concluded that to to use
use an an excessively large or or
The annualized costs of fuel and and capital, atat a t:.T
A r of 7 andand excessively smallt:.T
small AT is is a mistake. AtAt excessively large t:.Ts,ATs,
14F, are
are summarized and and compared in in Table 2.2. Though the the the capital saved is is much less than the the increase in in fuel costs.
total annual cost is is essentially unchanged over the the 7 toto 14F
14F Thermodynamic availability is is being wasted. At At excessively
A r range, there are
t:.T are some important differences. The The cost ofof ATs, the
small t:.Ts, the thermodynamic availability saved is is accompa-
for availability expended is
fuel for is only half
half as
as much at at a t:.T
A r of
of nied by a disproportionate increase in capital costs. Thus, design
ATs may be deemed to be "second
at excessively large or small t:.Ts
errors."
law errors."
Table 1 Costs of fuel and capital versus A
ATT (Sarna,
(Sama, 1983) What isis an
an excessively large or or small t:.T
AT depends on on the
the
nature of the process in in which thethe heat exchange occurs, the the
Delta T
DeltaT Cost Fuel Cost Capital Total Cost .6.A From
From % cost of fuel, the cost of heat exchangers, and the cost of capital.
~
F ~
^C $1 000
$1.000 ll.QQQ
S1.000 $1 000
$1.000 Min.
%
Dev.
1 0.556 58 5,867 5,925 4,754 406
ATs must be determined in
Excessive t:.Ts in each situation by experi-
2 1.111 117 2,933 3,050 1,879 160 or by procedures such as that used for the heat exchanger
ence, or
3 1.667 175 1,956 2,131 960 82.0
4 2.222
2.222 233
233 1,467
1,467 1,700
1,700 529
S29 45.2
45.2 described inin the foregoing.
foregoing.
5 2.778 292 1,173 1,465 294 25.1 In some heat transfer
transfer situations, however, availability is is ex-
ex-
6 3.333 350 978 1,328 157 13.4
g
i';;i ~l;';~~.r:~~~)i:~:~g1~1l;l;l;l;E~~~~;l;l;;l;l;:~g*;;;~~~g;$;~*l~~~i~~
7 3.889 409 838 1,247 76 6.5 pended unnecessarily and and without anyany benefit.
benefit. In
In such
such aa case,
case,
8 4.444 " "467 733 1,200 29 2.5
9 5.000 526 652 1,178 7 0.6 is indeed "lost" or
availability is or "destroyed," and and also repre-
~~;iljJ~c~~j~~l'il~:~?l;2~j.ll~"i)~;t!i7.*~:~1~ct~~~l;~'9~;~:":fVj!}~;j
10 5.556 584 587 1,171 0" 0 sents a second law error.
11
' 11 6.111 643 533 1,176 55" 0.4
12 6.667 701
701 489 1,190 19 1.6 Consider the
the transfer
transfer of heat from steam to to a cold process
13
13 7.222 760 451
451 1,211 40 3.4
'!~\z~fuk'mi!lJliJ\~3::}~,l!'lI~I~~~~E:4jJlI?~~:il!::&'3il~~~~li!>~?~I~'llIi~
14 7.778 818 419 1,237 66 5.6 as shown in
stream as in Fig. 3.3. The heat transfer
transfer could be be accom-
15 8.333 876 391
391 1,267
1,267" 9G
96 " 8.2 8.2 by either
plished by either low-pressure
low-pressure steam
steam or orhigh-pressure
high-pressure steam.
steam. InIn
16 8.889 935 367 1,302 131
131 11.2
n17 9.444 993 345 1,338 167 14.3 a plant where steam is is produced
produced by by extraction
extraction oror back-pressure
back-pressure
18 10.000 1,052 326 1,378 207 17.7
19 10.556 1,110
1,110 309 1,419 248 21.2 turbines, more fuel is used to produce the required high-pressure
20 11.111 1,169 293 1,462 291
291 24.8 steam than to produce the low-pressure steam. Thus, high-pres-
21
21 11.667 1,227 279 1,506 335 28.6
22 12.222 1,285 267 1,552 381
381 32.5 sure steam requires more availability and more fuel to to accom-
23 12.778 1,344
1,344 255 1,599 428 36.5
24 13.333 1,402 244 1,646 475 40.6 plish the same heat transfer. This, however, may not be a second
25
25 13.889
13.889 1,461
1,461 234
234 1,695
1,695 524
524 44.7
44.7 law error.
lawenor.

Journal of Energy Resources Technology

Technology SEPTEMBER 1995, Vol.
Vol. 117
117 / 181
181

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 H.P. Steam
H.P.Steam TSat.@H.P.
T Sat. @ H.P.
T
Fig. 3 Heat transfer by H. P. steam
The high-pressure steam, because of its higher temperature,
results in a higher b.TA r and a smaller heat exchanger. Thus, the
high-pressure steam's extra availability is expended to save
capital. Whether the trade-off
trade-off between availability and capital is
worthwhile depends on the relative values of fuel and exchanger
corrosive service, for example, where expen-
surface. In a very cOlTosive
sive materials are required, the use of the higher-pressure steam
might indeed be more economical.
Consider, however, the use of the same high-pressure steam
to accomplish the same heat exchange duty, as is shown in Fig.
4. Here, the high-pressure steam is throttled to a low pressure
before it is used in the heat exchanger. No use is made of of
the higher availability at the higher pressure. Availability is
destroyed in the throttling valve without any benefit. This is a
second law error.
Another, less obvious, example of a second law error is that
of unnecessarily matching streams of significantly
significantly different
different flow
heat capacities. Heat exchange is more thermodynamically re-
versible when it is between streams of similar flow heat capacit-
ies, i.e., as the temperature-enthalpy lines become more parallel.
Figure 5 depicts heat exchange between two streams of differ-differ-
ent flow heat capacities. The hot stream, having a smaller flow
heat capacity, has a steeper slope. To emphasize the point to
be made, a zero b.T A r approach temperature is chosen. Also
shown, as a dotted line, is a hot stream whose flow heat capacity
?hown,
is the same as the cold stream. Here too, the approach b.T
IS AT is
zero. Since it is parallel to the cold stream, the b.TA r is zero over
the entire length of the temperature-enthalpy line.
The same amount of heat, and the same amount of availabil-
ity, could be transfelTed
transferred by either of the hot streams to the cold
stream. The mismatched hot stream, however, suffers suffers a larger
decrease in availability. What happens to the difference?
difference? Is it
traded for a decrease in exchanger surface? In both cases, an
infinite heat exchanger area is required. Thus, nothing is ob-
tained for the extra availability used. The availability is simply
"destroyed." We can conclude, generally, that it is a second
law error to unnecessarily exchange heat between streams
whose flow heat capacities are mismatched.
When we have only one stream to be heated and only one
stream to be cooled, there is no choice. We must exchange heat
between them (but not to zero b.T)AT) regardless of the differences
differences
H.P. Steam TSat.@H.P.
T Sat. @ H.P.
Jl jf Destroyed B
T parabolic equation. For complex engineering problems, on the
I L.P. Steam TT Sat.@L.P.
Sat. @ LP.
Cold ^J^0^"00"^
H
Fig. 4 A 2nd law error
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T
H
Fig. 5 capacities
Mismatch of flow heat capacities
in their flow heat capaCIties.
capacities. Also, unless the hot stream is
condensing and the cold stream vaporizing, we cannot expect
temperature-enthalpy lines to be exactly parallel.
the temperature-enthalpy
However, when a number of streams are exchanging heat,
such as in a heat exchanger network, there may be choices that
reduce the mismatches between flow heat capacities in the heat
exchangers. In addition, we may be able to split a large flow
heat capacity stream to exchange heat with two or more streams
of smaller flow heat capacity. Flow heat capacity is an extremely
important design variable, and it should be considered in the
design of any heat exchanger network. We may have an oppor-oppor-
significant design decision. This opportunity
tunity to make a significant
should not be wasted!
A final and obvious guideline in choosing streams for ex-
changing heat in a heat exchanger network is that the streams
should be selected to minimize any large mismatches between
their temperatures.
Optimization of Designs
Since the second law governs all processes, one would expect
it to be used extensively in the optimization of designs. In fact,
fact,
however, the second law is not often used.
Three design optimization approaches will be discussed in a
generalized and philosophical manner:
1 optimization
optimization by
by combination
combination and
and permutation;
permutation;
2 optimization by mathematical modeling;
3 optimization using second law insights.
insights.
Is There a Global Optimum Design? Too often, in engi-
neering education, students are told that they must design only
exact economic optimum. To do otherwise would be
at the exact
off in search of the "Holy Grail" called
heretical; thus, they are off
global optimum.
the global optimum.
In this quest, they must invoke the sacred powers of science
and mathematics. However, engineering is not just science and
mathematics. Neither is it just a computer program, nor just
economics, nor just a handbook. Engineering
Engineering is also an art. The
engineer may be considered to be an artist, who uses science,
mathematics, computer programs, economics, handbooks, and,
one hopes, common sense to solve problems.
Unfortunately, only trivial problems have single optimum
solutions; for example, determining the minimum value of a
other hand, there is no such thing as a single optimum solution.
Suppose, for example, that we set out to design a living
creature that can fly-which
flywhich may not be as far-fetched
far-fetched as it
once seemed. Would there be one global optimum flying-crea-
flying-crea-
ture design? Would the single optimum design be a bat? A bee?
A bird? A fly? A flying horse? A horse fly? Or a whatever?
Among birds alone, there are about 9000 species in the world.
Is there a single best one?
Transactions of the ASME
 If
If Nature cannot decide on a global optimum flying creature,
how can we? How arrogant can man be to insist that he can
find the optimum solution in any but trivial situations? Is this
what we should be teaching our students? I regret that all too
often we are.
often
Suppose we asked a large group of engineer-artists to render
a painting of the same landscape. This is not a trivial problem,
especially for me. Without any doubt, my painting would not
be the optimum one. Suppose, also, that the group of engineer-
artists included a young Michelangelo along with Monet, Pi-
casso, Rubens, and van Gogh. Whose painting would be the
optimum one?
Painting a picture has been trivialized in what is called a
"paint-by-number"
' 'paint-by-number'' set. The entire canvas is broken down into
areas. Each number represents a differ-
a multitude of numbered areas. differ-
ent color paint, which is contained in a correspondingly num-
bered container. When the final numbered paint is applied to the
voila!we have a painting. My painting,
final numbered area, voila!-we
though perhaps improved by this method, would, of course, still
painted-by-number by the Mas-
not be nearly as good as those painted-by-number
inferior to their
ters. Theirs, on the other hand, would be much inferior
own original paintings.
However, we can go further. We can totally trivialize the
process by using a computer to paint-in each area. Then, I would
be able to produce, identical in all respects, the same painting
as Michelangelo. Without even needing to know anything about
what I was painting, I could render the "global optimum"
painting. Is this the Holy Grail for which we are searching?
The next logical step, of course, is to fire all the engineer-
artists and replace them with a global computer. Too bad- bad
young Michelangelo had a lot of potential. Perhaps, had he
been directed along a more sensible path, Michelangelo might
have eventually made some useful contributions to mankind.
The conclusion is clear. In complex systems, and often
often even
in apparently simple ones, the existence of a global optimum
fruitless.
is a myth whose pursuit is fruitless.
Optimization by Combination and Permutation. Access
to increasingly powerful
powerful computers over the last 30 yr has led
some to try to replace the "art" in process design by the work-
ings of an unthinking computer. This was especially true in the
design of heat exchanger networks (HENS) and is discussed
in some detail by Sama (1992).
All one needs to do, is to calculate the total annualized cost
of each of the possible combinations of heat exchangers that
can accomplish the required heating and cooling objectives.
The particular combination with the minimum cost can then be
identified, without any doubt, as the global optimum HEN. No
skill beyond that of making the calculations is required. These
calculations can, of course, be easily done by computers.
Where does the second law come in? In an optimization
problem involving heat transfer, should we not be using the
second law?
We impose the restriction that heat cannot be transferred
transferred
from a lower temperature stream to a higher one. Otherwise,
the lowest cost solution, which would inevitably require the
transfer of heat from a lower temperature to a higher one, would
be impossible. Thus, the second law is not being used in the
design process in a positive sense to find the optimum solution.
impossible an-
It is invoked only in a negative sense to avoid impossible
swers.
However, even in relatively simple HENS, there are often often
too many combinations and permutations for even a computer
to calculate. For example, Ponton and Donaldson (1974) sug-
the number of evaluations by a tree-searching algo-
gest that the.
rithm to guarantee the global economic optimum HEN ap-
(H,, X
proaches (n" X nJ!,
nc)\, where nil
nh is the number of hot streams,
nc the number of cold streams. For a modest HEN involving
and nc
heat exchange between 5 hot and 5 cold streams, the number
25
X 5)
of evaluations required is (5 X 5)!, X 10 25
!, or 1.55 X . This number
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Technology
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of evaluations does not include those combinations that allow
the splitting of streams. Stream splitting, which would result in
an essentially infinite number of possible combinations, is not
allowed in tree-searching computer solutions. Thus, as origi-
second law not used in this
nally envisioned, not only is the second'
optimization procedure, but second law insights, such as the
specifically
splitting of large flow heat capacity streams, are specifically
prohibited.
25
In addition, though most of the 1.55 X 10 25 combinations
would clearly be nonoptimum, could it ever really be expected
Only one, combination would be optimum? Be-
that one, and bnly
25
effort evaluating more than 10 25
sides, why expend all that effort bad
solutions?
In order to reduce the number of evaluations required, the
second law was finally used in the form of "heuristics," i.e.,
guidelines to be considered in the design process. Ponton and
Donaldson (1974) reported that good solutions could often be
found by using a single heuristic, with only hand calculations
required. However, even with the use of those heuristics, one
could never be entirely sure that the "global optimum design"
(which we have shown to be nonexistent) had not been over-
looked.
In retrospect, it is clear that the unquestioned belief
belief in, and
search for, a single-optimum solution in complex design prob-
lems is a mistake. It is equally clear that calculation of every
permutation is not the best
possible design combination and pelIDutation
way to optimize a design.
Optimization by Mathematical Modeling. Optimization
by mathematical modeling is obviously a valuable tool. Some-
refrigerated
times, as in the preceding optimization of a single refrigerated
heat exchanger, the second law is used in a direct, positive way
to develop the model. More often, however, the second law is
not used at all. Its extended use should be encouraged.
We have already identified
identified serious problems with mathemati-
cal modeling. The first is that usually the objective is to find
the single global optimum, which does not exist. The second is
often the model takes on a life of its own, so to speak.
that quite often
often considered to be a precise replication, and is no longer
It is often
simplified approximation of a complex
recognized as being a simplified
problem that has no exact solution. Who knows what the future future
costs of fuel, equipment, and money will be? Also, minimum
total annualized cost is often
often used as the measure of optimiza-
tion. This criterion is "blind" to the fact that there can be
significant differences
significant differences between solutions that have similar total
refrigerated heat exchanger, we
annualized costs. At a single refrigerated
found significant
significant differences
differences in the distribution of that cost
between fuel and equipment. In more complicated process de-
signs, the difference
difference may also be one of control, operability,
safety, etc.
The final design decision, after
after careful
careful consideration of the
results of the model, should always be made by the engineer.
The model should encourage thinking, not replace it. It should
be used to improve the judgment of the engineer, not discourage
his or her use of judgment.
Perhaps, however, the most important attribute of the model-
ing process is not optimization, but rather education. Our under-
standing of the heat exchange process was certainly enhanced
by the mathematical model developed earlier. I am firmly con-
understanding the process
vinced that understanding process
process is the key to good process
significant aid
design, and that mathematical modeling can be a significant
to that understanding.
There is, however, another limitation. Mathematical model-
ing usually deals with the optimization of the design parameters
for a given process structure, but does not normally consider
ethanol/
changes in the process structure itself. For example, an ethanol!
freezing,
water mixture can be separated by distillation, partial freezing,
semi-permeable membranes, and by other techniques. An appro-
priate mathematical model to optimize the more common dis-
tillation process may give us a false sense of security, and the
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SEPTEMBER 1995, Vol. 83
 wrong design, if in fact one of the other separation
sepai'ation methods
were more suitable for the particular separation at hand.
Big improvements in process design are often a result of of
changes in the structure of the design, but mathematical model-
ing does not usually address such changes.
Optimization Using Second Law Insights. The most im-
portant tool we have to understand processes is the second law.
Wherever and however possible, the second law should be used
guarantee a process de-
for guidance. That guidance can often guarantee
sign improvement.
For example,suppose
example, suppose it is found that high-pressure steam
has been unnecessarily throttled before
before being used in a heat
exchanger, as in Fig. 4. This was identified
identified as a "second law
error," because availability was used up without any benefit, benefit,
i.e., availability was destroyed. We know that elimination of
the throttle will improve the design. In this case, the cost of the
heat exchanger will be reduced without any increase in the use
trade-off between the cost of fuel
of fuel. Note that this is not a trade-off fuel
and cost of capital. It is the elimination of a second law error.
Whenever we find and eliminate a second law error in a
process, we know that the process will be improved. Sometimes,
as was the case here, the cost of equipment will go down.
Sometimes it is the cost of fuel that goes down. Sometimes
both the cost of equipment and the cost of fuel go down! Thus,
significant improve-
elimination of second law errors can make significant
ments in the design of a process.
Sarna
Sama et al. (1989) proposed a set of l3 13 "commonsense
"commonsense
second law guidelines" that can be used as an aid in detecting
and avoiding second law errors. These guidelines were used to
improve the design of a dual-pressure nitric acid plant. Nitric
acid is produced from the oxidation of ammonia. This is an
exothermic reaction, and it is possible to export power from the
process. The original design exported 3965 kW of electrical
following)
power. Two second law errors (nos. 3 and 6 in the following)
were detected and eliminated. The result was an increase in
power output to 5325 kW, an increase of over 34 percent, and
a reduction in capital cost due to the elimination of a heat
exchanger.
The 13 commonsense second law guidelines proposed by
Sarna
Sama et al. (1989) (with slight changes shown in italics) are:
1 Do
Do not
not use
use excessively
excessive/v large
large or
or excessively small ther-
excessively small ther-
modynamic driving forces in process operations.
2 Minimize the mixing of streams with differences
differences in tem-
perature, pressure or chemical composition.
3 Do not discard heat at high temperatures to the ambient,
ambient,
or to cooling water.
4 Do not heat refrigerated
refrigerated streams with hot streams or
with cooling water.
5 When choosing streams for for heat
heat exchange, try to match
match
streams where the final temperature of one is close to
the initial temperature of the other.
6 When exchanging heat between between two streams, the ex-
efficient if the flow
change is more efficient flow heat capacities ofof
the streams are similar. If If there is a big difference
difference be-
tween the two, consider splitting the stream with the
flow heat capacity.
larger flow
7 Minimize the use of intermediate heat transfer fluids fluids
when exchanging heat between two streams.
8 Heat (or refrigeration) is more valuable, the further its
temperature is from the ambient.
9 The economic optimum !:::.T AT at a heat exchanger de-
creases as the temperature decreases, and vice versa.
10 Minimize the throttling of steam, or other gases.
11
11 The larger the mass flow, the larger the opportunity to
save (or to waste) energy.
12 Use simplified
simplified exergy (or availability) consumption cal-
{or availability)
culations as a guide to process modifications.
modifications.
13 Some second law inefficiencies
inefficiencies cannot be avoided; oth-
ers can. Concentrate on those which can.
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These 13 guidelines are based on second law insights, as well
as on common sense. Note, also, that the first guideline, as well
as nos. 5, 6, 8, 9, and 10, have already been discussed in the
simplified exergy (or availability) calcula-
present paper. The simplified
be'done
tions, called for in guideline 12, can usually be done without
the use of entropy. Equations to do so at heat exchangers, com-
pressors and turbines, and for changes of state of ideal gases,
Sama et al. (1989).
are derived and presented in Sarna
The approach to process optimization using these guidelines
is as follows:
follows:
1 First,
First, understand
understand what
what the
the process
process is
is about.
about.
2 Then, design the process based on second law considera-
tions.
3 Next, look for second law errors in the design. They are
of usually easy to identify.
identify.
4 Change the design to eliminate all second law errors.
5 When all second law errors are eliminated, perturb the
thermodynamic driving forces up or down to make suit-
able trade-offs
trade-offs between the use of fuel and the use of
of
capital.
6 Look again for second law errors and, if need be, repeat
the process.
The big improvements in a design will come from detecting
and eliminating second law errors. This oftenoften changes the struc-
Trade-offs due to perturbations of thermody-
ture of the design. Trade-offs
namic driving forces, while important, do not change structure
significant.
and are not likely to be as significant.
The nature of your design will depend, on your ability to find
second law errors and, on your ability to respond to them.
Sometimes it will be very easy; sometimes it will require a bit
of sophistication. For a simple problem, you will arrive at the
same solution as any other reasonably competent engineer-art-
ist. For a complicated problem, there will be many optimal
Michaelangelo's,
solutions. Your design may not be as good as Michaelangelo'S,
but you will have learned a great deal by executing it. Your
next design will be better. With practice it will be much better
than a "paint-by-numbers" design.
The l313 commonsense second law guidelines are easy to use,
and look deceptively simple; however, they have proven to be
powerful.
quite powerful.
For example, Sarna
Sama ((1992)
1992) showed how easily the guidelines
could be used to solve a heat exchanger network problem, the
"Front End of a Specialty Chemical Process," often posed in
pinch technology articles. This example has been presented so
often (Boland and Linnhoff, 1979; Linnhoff, 1981;
often 1981; Linnhoff
Linnhoff et
al., 1982; Linnhoff, 1983a, b; Janet and Amarnath, 1991) that
aI.,
it is almost a trademark for pinch technology.
The initial design in this problem has an obvious second law
error. The splitting of a large flow heat capacity stream, per
guideline 6, solved the problem. This was done essentially by
inspection. Moreover, this approach provided clear insight into
how the original process design was flawed. Pinch technology,
though it resulted in the same solution, did not provide any
such insight. On the other hand, since the solution requires
stream splitting, this problem could not have been solved at all
by a computer with a tree-searching algorithm.
Melli et al. ((1990)
1990) used the same l3 13 commonsense guidelines
as the strategies in a computer-driven, interactive, artificial intel-
(Al) program to design and optimize the process design
ligence (AI)
of plants. This program, SYSLAM, was used to design a power
plant; and "clearly outwitted" a previous AI Al program called
P-SLAM. More recently, Melli and Sciubba (1992) discussed
their 3rd generation AI Al program, COLOMBO. They are still
using the same l3 13 commonsense second law guidelines for their
strategies. In both papers, they state that these guidelines "." . .. .
simplified formulation of
represent, in our opinion, the best simplified of
'second law thinking' currently available."
Thus, the efficacy
efficacy of using the second law in process design
and optimization has been clearly established. The explicit
explicit use
Transactions of the ASME
 of second law insights should be central to the design process. of the models. Mathematical models can can also give important
Optimization using the 13 commonsense second law guidelines process insights. However, mathematical optimizations are are
is aa step in
in the right direction. trade-offs between capital costs and
sometimes merely trade-offs and fuel
fuel
costs, rather than optimization of the design structure itself. Big
improvements in in designs usually come from the latter.
6 Conclusions
Conclusions The removal of of second law errors from aa given design guar-
The second law governs all changes in in Nature. It It should be antees an improved design: one in which fuel cost, capital cost,
central toto the design of of heat exchangers;
exchangers, heat exchanger net- or both will be saved. A A design which has no second law errors
works, andand processes.
processes. However,
However, the thesecond
second law law isisgenerally
generally may be considered to be an optimal design, and should be the
ignored as aa design tool. of optimization by means of
objective of of the second law.
A second law analysis of of aa refrigerated
refrigerated heat exchanger was The second lawlaw should notnot continue to
to be
be ignored in
in the
the
made. A A plot of of the total annualized cost of of fuel and capital as as design and optimization of processes. Rather, the use of second
a function of the boT AT between the refrigerant
refrigerant and the condensing
condensing law insights should be aa fundamental
fundamental tool used by all engineer-
stream is is very flat in in the vicinity of of the optimum. Differences
Differences artists.
between calculated total annualized cost over aa range of of boTs
ATs
are much less than the uncertainty in predicted predicted costs of of fuel,
fuel, Acknowledgment
equipment or or capital. As As aa result, the the optimum boT AT is is not
not aa The author is grateful
grateful to
to Professors Jan Szargut and George
singular value, but, rather, aa range of values of of D..T
AT over which Tsatsaronis, without whose encouragement this paper would
there isis no significant
significant difference
difference in in total annualized cost. never have been written. All positions and opinions in this paper
There are, however, significant
significant differences
differences in the distribution are, however, solely the responsibility ofof the author.
of this cost. At the low end of of this D..T
AT range, less is is spent for Thanks are
are due
due to
to my
my colleague and and friend, Leonard F. F.
fuel and more is is spent for for capital. This should be be the design Meuse, Jr., Director of
of The College of of Engineering's Writing
AT when energy saving is
boT is paramount. At the high end of of this Improvement Workshop at at The University of of Massachusetts
AT range, less is
boT is spent for for capital and and more for for fuel. This thoughtful questioning and careful
Lowell. His thoughtful careful review of several
should be be the design D..T AT when saving construction capital is is to aa significantly
preliminary drafts led to significantly improved manuscript.
paramount. Thus, minimization of of the total annualized cost, by
itself, should not be the only criterion for optimization. References
On the other hand, to to design at at aa boT
AT significantly
significantly below or or Boland, D., and Linnhoff, B., 1979, "The Preliminary Design of Networks for
above the optimal D..T A r r arange
n g e would be aa mistake. At too Iowa low a Heat Exchange by Systematic Methods," The Chemical Engineer, pp. 222-228.
AT, the
boT, the extra
extra cost
cost of
ofthe the equipment
equipment required
required isismuch
much larger
larger Comley, W., 1978, Stone and Webster Engineering Corporation, personal com-
than that of of the fuel saved. At At tootoo high
high aa D..T,
AT, thethe cost
cost of
ofthethe munication.
extra fuel used is much larger than that of the equipment saved. Amamath, A,
Janet, P., and Amarnatb, 1991, "Putting the Pinch on Energy Costs," EPRI
A., 1991,
Journal, July! Aug., pp. 24-31.
July/Aug., 24-31.
To design at at too high or or too Iowa AT1 is
low a D..T is aa second
second law law error.
error. Linnhoff, B., 1981,
1981, Esso Energy Award Lecture.
Second law insights in in the
the design process are are often
often direc-
direc- Linnboff,
Linnhoff, B., 1983a, "New Concepts in Thermodynamics for Better Chemical
tional, and not quantitative. The second law can dictate design Process Design," Proceedings
Proceedings of the Royal
Royal Society
Society of Londo/!,
London, Vol. 386, No.
1790, pp. 1-33.
1-33.
often without the use of availability or exergy calcula-
decisions, often Linnhoff, B.,B., 1983b, "Short Course on on Heat Recovery Network Design,"
tions. Disregard of of such design dictates are second law errors. Course Notes, Stone and Webster Engineering Corporation.
The list of of 13 commonsense second law guidelines proposed Linnhoff, B., Townsend, D. W., Boland, D., D Hewitt, G. F., Thomas, B. E. A.,
by Sama et et al. (1989) may be be used to to easily identify
identify second Guy, A. R.,
R., and Marshland, R. R. H., 1982, A A User Guide onon Process
Process Integration
Integration
law design dictates and second law errors. for the Efficient
for Efficient Use
Use of
of Energy, Institution of
of Chemical Engineers, Rugby, U.K.
Melli, R., Paoletti, B.,
B and Sciubba, E., 1990, "SYSLAM: An Interactive Expert
There is generally no singular optimum design. Instead there Approach to Power Plant Design and Optimization," Proceedings
System Approacb Proceedings of of the
is aa set of optimal designs whose number increases as the com- Florence
Florence World EnergyEnergy Research
Research Conference, Pergamon Press, pp. 371-385.
plexity ofof the problem increases. As aa result, the search for for aa Melli, R., and Sciubba, E., 1992, "Second-Law Based Synthesis and Optimiza-
is both futile and misleading. Engi- tion of Thermal Systems: A Third Generation Code," Proceedings
Proceedings of
of the Interna-
Interna-
global optimum solution is tional Symposium
Symposium on on Efficiency, Costs, Optimization
Optimization and Simulation
Simulation of Energy
Energy
neering is is an
an art.
art. Thus,
Thus, we we should
should expect
expect that
that optimal
optimal designs
designs Systems, ECOS '92, Zaragoza, Spain, ASME, pp. 241-247.
executed by different
different engineer-artists will be different. different. Ponton, J.J. W.,
W andand Donaldson, R. R. A
A. B.,
B., 1974, "A"A Fast Method for for The
In fact, different
different optimal
optimal solutions requirement for the
solutions are aa requirement Networks,'' Chemical Engineering
Synthesis of Optimal Heat Exchanger Networks," Engineering Science,
Science,
Vol. 29, pp. 2375-2377.
appropriate design of of complex processes. If each design pro- Sarna,
Sama, D. A, A., 1983, "Cost Savings Through Lost-Work Analysis at at Heat Ex-
duced by by aa group of of engineers is is identical, wewe can conclude changers," Energy
Energy Progress, Vol. 3, No.4,
No. 4, pp. 212-219, Dec.
that either thethe problem
problem isistrivial,
trivial, oror(as
(aswas
was found
found with
with the
the Sama, D. A,
Sarna, A., 1992, "A
"A Common-Sense 2nd Law Approach to Heat Exchanger
computer generated paint-by-numbers landscapes) that at at least Design," Proceedings
Network Design," Proceedings of the International
International Symposium
Symposium on on Efficiency,
Efficiency,
of the engineers are working below their capabilities. Optimization and
Costs, Optimization and Simulation
Simulation ofofEnergy
Energy Systems,
Systems, ECOS
ECOS '92,
'92, Zaragoza,
Zaragoza,
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What is is most noteworthy about this conclusion, is is that itit isis Sarna,
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Journal of Vol. 117 / 185
SEPTEMBER 1995, Vol.

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