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COMBUSTION AND FLAME 24, 89-98 (1975) 89

Asymptotic Theory for Ignition and


Extinction in Droplet Burning
C. K. LAW
GeneralMotors Research Laboratories, Warren,Michigan 48090

The quasi-steady diffusion flame structure in droplet burning is analysed, in the limit of large acti-
vation energy, for a one-step Arrhenius reaction in the gas phase. The characteristic ignition-extinction
S-shaped curve is produced with segments of it corresponding to a neatly frozen flow regime, a partial
burning regime, a premixed flame regime, and a nearly equilibrium regime. Critical Damk6hler num-
bers for ignition and extinction, as well as correction factors to the mass evaporation rate due to f'mite
activation energy, are obtained. Close mathematical and physical analogies exist between the present
problem and the counterflow problem recently analysed by Li~dn such that through appropriate
transformations most of his numerical results can be readily utilized.

1. Introduction cal time. Perturbations in the mass evaporation


Studies of the influence of f'mite gas.phase chemi- rate and other parameters of interest were ob-
cal reaction rates on hydrocarbon droplet evapora- tained. However, asymptotic analyses by treating
tion, with and without an envelope diffusion D as the perturbation parameter are incapable
flame, have been motivated by the needs to of defining ignition and extinction conditions.
establish ignition-extinction criteria as well as to Recently Lifi~n [4] analysed the structure of
estimate their effects on the evaporation rate, the counterflow diffusion flames, in the realistic
flame standoff distance, and the flame tempera- limit of large activation energies, 1 by the method
ture. Such data are important, for example, in of matched asymptotic analysis. The entire range
the design of liquid propellant rockets, oil burners of the Damkbhler number is covered and the
and internal combustion engines in which short characteristic S-shaped curve emerges by plotting,
ignition and overall evaporation times are desired. say, the maximum temperature vs D. Segments of
Two basically different approaches have been this curve correspond to a near frozen regime, a
adopted in a theoretical analysis of the problem. partial burning regime, a premixed flame regime,
The first approach involved approximating the and a near equilibrium regime, as the maximum
Arrhenius effect in an ad hoc manner. Hence temperature in the flow varies from the ambient
Tarifa et al. [1] assumed the temperature distri- temperature to the adiabatic flame temperature.
bution within the flame zone to be of a given Lifi~n's approach will be adopted here for a
form, whereas Peskin and Wise [2] approximated similar analysis of the diffusion flame structure of
the gas-phase heat release by a delta function. A droplet combustion. Both these problems involve
second approach, undertaken by Fendell [ 10],
for the similar problem of stagnation point diffu-
sion flame, and by Kassoy and Williams [3], in- l The term "large activation energies" is somewhat mis-
volved solving the exact conservation equations leading because the large parameter in the problem is the
by regular or singular perturbation technique, ratio of the activation energy (divided by the gas constant)
to a characteristic temperature in the flow field. There-
using the DamkiShler number D as either the small fore, the analysis is valid even for small activation energies,
or the large parameter, where D is defined as the provided the characteristic temperature is also sufficiently
ratio of the characteristic flow time to the chemi- low.

Copyright © 1975 by the Combustion Institute


Published by American Elsevier Publishing Company, Inc.
90 C.K. LAW

nonpremixed combustion in one-dimensional k


ao + bF -~ pP ,
flow; the only differences are of flow geometry
and the existence of condensed phase evapora- is assumed, where k is given by an Arrhenius rate
tion during droplet combustion. It will be shown law with a constant pre-exponential factor B'.
that, through appropriatetransformations, the We further assume that the reaction is first order
governing equations for droplet combustion can with respect to the fuel and the oxidizer concen-
be cast in a form bearing great similarity to those trations.
of the counterflow problem. In fact, the final Several of the above assumptions are made only
results for all but the near frozen regime are to simplify algebraic details so as to illustrate the
identical in the transformed coordinates such effects of finite activation energy as lucidly as
that most of the numerical results obtained by possible. The mathematical analysis outlined be-
Lifidn can be readily utilized. It may be of low can be similarly carried out by incorporating
interest to note that such close analogy also certain transport coefficient variations [3], by
exists for the stagnation point boundary layer letting the respective reaction orders to differ from
flow [5]. unity, and by allowing B' to have a general power
For easy comparison, the nomenclature and law dependence on temperature.
terminology of Ref. [4] will be adopted here
wherever possible. Familiarity with Ref. [4] is
also assumed. In fact the purpose of the present
paper is simply to illustrate the close analogy B. GoverningEquations
between the two problems and how results from The conservation equations for oxidizer o, fuel F,
Ref. [4] can be applied to the droplet problem. and energy T can be written as
Detailed derivation and discussion of results,
which can be found in Ref. [4] or [6], are 2-tyo}=£{yF}=-£{Tt=w , (1)
omitted here.
The formulation of the problem is presented where the operator
in the next Section. The flame structures are
analysed in Section III, which is followed by £=Md 1 a [ r 2 dr] (2)
Section IV for the conclusions. ?dr r 2 dr '

the production term


H. Formulation
Dy°YF exp(-Ta/T ) (3)
A. Assumptions w - T2M2
The combustion process is assumed to be quasi-
steady, isobaric and spherically symmetric. We the non-dimensional mass evaporation rate
further postulate that radiation effects are
negligible, that the heats of combustion and
vaporization are constants, that Fick's law for M = (o'v'r '2)/ (o;.o..r 's)' (4)
diffusion velocities is valid, that heat capacities
Cp and thermal conductivity coefficients ~' are The Damki~hler number
constants, and that the Lewis number Le =
p '0 'Cp'[X 'is unity, where 0 'is the gas density
and d'is the binary diffusion coefficient. p'ooo'~w' t aa , (s)
Quantities with primes are dimensional, with-
out primes non-dimensional. A one-step
and
Arrhenius irreversible reaction, with heat release
per unit mass of fuel consumed being -Q', and
whose stoichiometry is defined by r = r'/r's, T ~
C ;p ~ T t
/ Q ,# L = L'/Q'. (6)
ASYMPTOTIC THEORY FOR DROPLET BURNING 91

In the above equations, y o is the oxidizer mass in T s. It can be shown, however, that such a
fraction divided by the stoichiometric mass ratio change results in a uniform increase in the tem-
v of the oxidizer to the fuel, r' is the radial dis- perature distribution in the frozen region by a
tance, and v', the radial velocity, L ' is the constant amount equal to the perturbed part of
specific heat of vaporization, W; is the molecular I s , and does not affect the ignition conditions
weight of species L ~' is the gas constant, and determined therein.
Ta, the activation energy for the gas phase
reaction. Subscripts s and o. denote conditions C. Reduced Governing Equations
at droplet surface and ihfinity, respectively. Defining
The boundary conditions for Eq. (1) are
x = 1 - exp(-M/r), (14)
r = O*: y o "= O£ , (7)
and using the Shvab-Zhedovich approach, Y o and
yF=0, (8) Y F can be expressed as functions of T and x. The
analysis is then reduced to the solution of a
T=TO*; (9) single second-order differential equation for T as

r=l: dy o/dr = M y o , (1 O)

dY F/dr = -M( 1-y F) , ( 11 )


exp(-TJT), (15)
dT/dr = ML , (12) with the boundary conditions
T = T s = constant. (13)
x=O: T= To., (16)

The above seven boundary conditions are used x=xs : r= r ~ . (17)


to solve the three second order differential
equations and to obtain the parameter of interest, In the above
M.
In Eq. (13) the uniform droplet temperature Y o = ot (l-x) + T f - T , (18)
T s is assumed to be a constant. An alternate ex-
pression for T s is the Clausius-Clapperon equa- YF = x + Tf - T, (19)
tion which relates the equilibrium fuel vapor
concentration at the droplet surface to T s. Then with
Eq. (13) is the zeroth order solution with Ts
commonly known, in the case of pure evapora- TI = T o . - t3x, (20)
tion, as the prevailing "wet-bulb" temperature.
It has been shown [7] that, during evaporation where the important parameter/~ is given by
in a hot ambient atmosphere or during burning,
T s is very insensitive to changes in the ambient /3= To.- Ts + L , (21)
temperature, hence the assumption that T s is a
constant (usually taken to be the boiling point the location of the droplet surface by
of the fuel) to all orders of the following per-
turbation analysis is expected to be valid. During x s = 1 - exp(-M), (22)
equilibrium evaporation in a low Too atmo-
sphere, assumed to exist in the nearly frozen and the droplet evaporation rate by the relation
flow regime to be analysed, changes in To* can (clT/dx) x = - L exp(M). (23)
produce correspondingly large perturbations S
92 C.K. LAW

Close resemblance exists between the reduced where e is an appropriate small parameter of ex-
governing equations of the present formulation pansion and the index i signifies the perturbation
and those of the counterflow problem [4]. The order. Xflame is the location of the flame in the
production term in Eq. (15) differs mainly in the zeroth order approximation. The constants a/and
expression for x as a result of different flow con- b i are to be found through matching with the
figurations. The absence of the T a term in the inner solutions of the flame region.
denominator, in the counterflow problem, is due Finally, expressing M as
to the assumption of a constant density flow.
Whereas this extra T 2 term in Eq. (15) does not
M = o~ eiM., (26)
complicate the ensuring mathematical derivation, i=0 z
it can be easily removed by allowing B' to be
proportional to T '2. and by using Eqs. (22), (23) and (25), the i th per-
We further note that in both cases the
turbation to the mass evaporation rate can be
boundary conditions for the differential equa-
found. In particular the zeroth and first order
tions for T are the values of T specified at the expressions are
two boundaries, although now the fuel is located
at x s < 1 instead of at 1. Finally, the expressions
Mo=ln{l+(ao-Ts)/L}, (27)
f o r y o andy F are identical in both cases. The
parameter/3, which is the difference in the
boundary temperatures in the counterflow M l = % I(a o + L - Ts). (28)
problem, is now increased by an amount L due
to the additional heat needed for vaporization. In the following we shall determine the asympto-
tic solutions of Eqs. (15), for large values of
D. Temperature Distribution in the Diffusive-Convective Ta/Tflame, with a, 13,L and Too being known
Regions and of the order of unity, and with the DamkiShler
The production term in Eq. (15) is expected to number ranging from zero to infinity. The bound-
be important in a flame zone where T is high, ary conditions for Eq. (15) for the flame zone
hence the exponential term is not small. However, analysis are obtained through matching with the
a slight reduction in T by moving away from this outer solutions given by Eqs. (24) and (25).
diffusive-reactive region of high temperature will
freeze the chemical reactions, therefore rendering
the production term exponentially small. In IlL Flame Structure Analysis
these regions the transport of mass and heat are The four types of diffusion flame structures
by diffusion and convection only. Furthermore, identified by Lifi~n [4] for the counterflow
Eq. (15) indicates that the temperature is linear problem also exist for droplet evaporation. When
in x, in such cases, to all orders of perturbation. a reduced Damkbhler number is properly defined
Evaluating such a temperature expression at x = 0 for each of the four regimes, the derivation and
and x = x s for the regions in the oxidizer and solutions for both problems are identical with
the fuel sides of the flame, respectively, and by the only exception of the first and higher order
Using Eqs. (22) and (23), the following general solutions for the nearly frozen regime. Hence
expressions are obtained [6], in the following only those solutions that are
different from Ref. [4] will be elaborated, the
rest will only be briefly discussed.
T=T,~+ b x, for(Xflame--x)/e>>l, (24) In the limit of Ta ~ 0% three types of zeroth
order flows are possible, depending on if both
and the fuel and oxidizer, or if only one of them,
exist in the flow field. Lifi~n called the first
r=(roo-13) + / ~ eia/~ (l-x), for(x-Xflame)/e~>>l, case as frozen flow and the latter two as
\i=0 )/ (25) equilibrium flows (with eithery ° = 0 or YF = 0).
ASYMPTOTIC THEORY FOR DROPLET BURNING 93

As the flame temperature varies from the bound- M, = o I (**)ltd. (35)


ary temperature Too to the adiabatic flame tem-
perature T e, the following four combustion Equations (31), (33) and (35) are the same as
regimes are encountered. the corresponding results in Ref. [4] with the only
exception of the factor ×4 instead of X2 which
A. Nearly Frozen-Ignition Regime results from different geometries in the two cases.
The entire flow field is frozen to the zeroth order, It may be noted that had we allowed for a per-
with the mass evaporation rate given by turbation in the droplet temperature, say eTst,
the expression for 01 (oo) will simply be increased
My = In (filL) (29) by a constant amount Tst. The rest of the results
are unaffected.
which is just the classical result for pure evapora- Equations (3 I), (33) and (35)have been solved
tion of droplets. numerically by using the technique of quasilinear-
When weak, but finite chemical activities occur, ization and finite difference [11]. Figure 1 shows
the temperature rises slightly above its frozen some typical solutions for 3 = 0.3. For a given 3, by
value, and is responsible for ignition. It is ex- plotting 01 (oo) vs A, the lower, ignition branch
pected that although chemical reactions are of the S-curve is obtained (Fig. 2). The values of
frozen near the droplet, as the fuel vapor is A, corresponding to the vertical tangents to these
transported outward the residence time increases, curves, are the reduced ignition DamkShler num-
hence favoring chemical activity. We therefore bers AI. Hence a universal curve of AI vs 3 is
proceed, in the same manner as Appendix A of
ReL [4], to analyse the structure of this diffusive-
reactive zone by expanding near x = 0 through • - 0.3
the inner variable × = x/e, where e = T ~ / T a < < 3
is the small parameter for expansion.
By assuming the temperature distribution for
this inner, flame zone as

T = Too + e I 0 1 (X)-/3X] + e202 + . . . . (30)


el

°I
~11 I I I A°|
I I t J I
Eq. (15) becomes "0 2 4 6 8 10 12 14 16 18
x

x 4 (d 2 01/dx 2) = -A(x-O,) exp(0,-3x), (31) Fig. 1. Typical solutions of the function 01(X) for/3 = 0.3
and various A's.
where A is the reduced Damkbhler number
obtained, as is shown in Fig. 3. For small values of
(1-/3), Lifidn [8] has shown that an excellent
A = a D o (eToo) "2 exp(-Ta/Too) (32)
approximation for AI is
and D O is the zeroth order expansion of D.
Matching Eq. (30) with the outer solutions
A, = (I +o.531t~)/(I-~) (36)
Eqs. (24) and (25), and by using Eq. (27), we
obtain the boundary conditions for Eq. (31) as
Therefore for a given t, an ignition Damkbhler
o, (0) = o, (33) number D o can be determined by substituting the
value of AI found from either Fig. 3 or Eq. (36)
(dO ~NX)X_~o
o = O, (34) into Eq. (32).
The case o f t = O(e) and x = O(1) analysed by
as well as the perturbation in the mass evapora- Lifidn was not found to exist in the present prob-
tion rate lem. The expressions for d2Ol/dx2 are singular
94 C.K. LAW

at x = 0 for both problems, but the singularity is The temperature perturbation in the frozen flow
milder for the counterflow problem, hence con- region towards the oxidizer side is
vergence of the solutions to 01 (0) = 0 apparently
is possible. For the present case the singularity is B 1 = 2 { ( a + {O/Yob + ([3- I )/Y Fb
much stronger (d2 0 Jd.x 2 ~ x "3, as x ~ 0),
rendering convergence impossible. - 2 [1+ 2/ln(1-xb) ] /(1-Xb) }. (39)
B. Partial Burning Regime With Ao and B t defined by Eqs. (37) and (39), it
In this regime a weakly burning flame separates can be shown that Eqs. (41) and (42) of Ref. [4]
two regions of frozen flows such that leakage of are now respectively replaced by
both reactants through the flame is possible to
all orders of the analysis. The present analysis is
DbYobYFb exp(-Ta/T b)
identical with that of Ref. [4] and will not be
repeated. The reduced Damk6hler number is now
given by = (ra[2) 1-Xb)(rb-Too)/x b
l
Ao ={DbYobYFb exp ('Ta/Tb)}/ [ln(1-Xb)]4exp(-*m ), (40)
and /

{Ta(l-Xb)2[ln(1-Xb)]4}, (37) %= 'In 4 +x b .{(a+f3)/Yob+

where x b and Tb are related by -2 [1 +2/In (1-Xb) ]/(1-Xb)}. (41)

x b = { 2 + [3/(Tb -Too) } -1 (38) By plotting the flame temperature T b vs the


Damki3hler number D b (Eq. (40)) the ignition-

Ol{eO)

109

6
5
1

2 I ! I I i t It I l I I I I llll l l I I I I TM l i I i I I i Jl
2 3 4 5 6789100 2 3 4 5 6789101 2 3 4 $ 67891u ~ 2 3 4 5 6789103

Fig. 2. Maximumperturbed temperature, 01 (co),vs A for various13.


ASYMPTOTIC THEORY FOR DROPLET BURNING 95
~m

2--

AI
! /

10C
~1 ~2 ~3 ~4 ~5 ~6 ~7 ~8 ~9

Fig. 3. Ignition Damk6hler number, AI, vs ~, for the nearly frozen regime.

extinction S-curve emerges. Detailed discussions Mb = lnI [3/[(1-2Xb)L] } . (42)


on the characteristics of the different branches
of this curve are given in Ref. [4]. A slightly more general formulation allowing for
Finally, since the problem for this regime was such a perturbation is detailed irr Ref. [6].
posed such that there is no temperature perturba-
tion in the frozen region in the fuel side, the mass C. Premixed Flame Regime
evaporation rate is given, to all orders, by In this regime, to the zeroth order, leakage of only
96 C. K. LAW

one reactant through the flame is possible, the


oxidizer if a + 2/3 > 1, the fuel if a + 2/3 < 1.
)
For higher orders in e = Ta/Tp small leakage of
the second reactant is also possible. Extinction
may occur when this leakage becomes excessive.
When a reduced Damkbhler number p is properly
defined, complete analogy again exists with the such that Eq. (67) of Ref. [4] is now replaced by
corresponding case of Ref. [4]. For o~+ 2/3 < 1,
Po is given by D,/opexp(-r,/rp
Po = ln l [2DpY Fp (Xp e/a)2 exp(-Ta/Tp)l / = (1/2) (1-/3)(1-Xp)/(m exp(-nm), (50)

where
[Tp (1-xp)2 ( l n (1-xp)) 41 I , (43)
m = 1 -(Tp-Too+~), (51)
such that Eq. (59) of Ref. [4], which relates the
flame temperature Tp with the Damkt~hler num- and
ber Dp, is now replaced by
Tp = Too + (1-/3)xp. (52)
Btp'Fpexp(-Ta/rp)
Since for this case the problem is posed such
that there is no temperature perturbation in the
frozen region of the fuel side, the mass evapora-
= (1/2) iv n( tion rate is given, to all orders, by

exp(-nm), (44) Mp = ln{ U/3+xp[(l-xp)]/L}. (53)

where The term nm in Eqs. (44) and (50) is a function


of m, hence T.. Lifi~nobtained approximate
m = (Too + o~- Tp)[OL, (45) expressions [ 8 for (nm) which were found to
agree with his numerical results within a few per-
and Xp and Tp are related by cent. Hence for -0.2 < rn < 0.5:
Tp = Too + ot - (e +/3)xp. (46) nm = 1.344m - 4m 2 (1-m)/(1-2m) + 3rn a
The zeroth and first order mass evaporation rates - In (1--4m 2); (54)
are

and for small positive and all negative values of m


Mp = ln {(et + /3)/L } , (47)
nm = -ln (0.6307 m 2 - 1.344m + 1). (55)
and
Substituting Eqs. (54) or (55) into Eqs. (44) or
Mt = -Y : (oo)/(l-Xp)l(°t+/3). (48) (50), a relation between T and D is obtained
P.
which, when plotted, results in an S-shaped curve.
Figure 7 of Ref. [4] shows y t (oo) as a function The upper branch of this curve is of interest most
of re. of the time in this regime, although ignition may
For t~ + 2/3 > 1, Po is given by also occur when (1-/3) is small. Detailed discus-
ASYMPTOTIC THEORY FOR DROPLET BURNING 97

sions on the implications of the analysis can be Equation (60) is just the classical flame sheet re-
found in Ref. [4]. sult for bipropellant droplet combustion (see, for
example, Ref. [9] ). The term lira (/~1-[) as func-
D. Near Equilibrium,Diffusion Flame, Regime
In this regime, to lowest order of approximation, tion of 8o for various 3' can be found in Fig. 11
the flame acts as a complete sink for both the of Ref. [4].
fuel and the oxidizer. For higher orders slight
leakage of both reactants are possible, and is IV. Conclusions
Exact mathematical correspondence between the
responsible for extinction. Complete agreement
is obtained with the counterflow problem when present droplet problem and the counterflow
the reduced DamkOhler number is defined as problem of Lift,in exist for the partial burning,
premixed flame, and near equilibrium regimes by
properly identifying a corresponding reduced
60 ={4Do(T2e/Ta)a/Te2/~n(l+ot)] 4}
Damkt~hler number in each case. For the near
frozen regime, due to effects of different geome-
exp(-Ta/Te), (56) tries, close but not exact correspondence was
found for the case x = O(e) and/3 = O(1). The
where the adiabatic flame temperature is case x = O(1) and/3 = O(e) obtained by Lifi~inwas
not found to exist in the present problem.
Te = T.. + (1-/3)a/(1 +~,). (57) Such close analogy is expected since both
problems involve non-premixed burning in one-
Lifi~n obtained an approximate analytic ex- dimensional flow. The effects of different geome-
pression for the reduced extinction Damkt~hier tries can be mostly eliminated through proper
number transformations whereas the presence of the con-
densed phase evaporation process is accounted
8oF, = e { (1-7) - (1-3') 2 + 0.26(1-3,) 3 for by incorporating the heat of vaporization L
in the boundary temperature difference parame-
+ 0.055(1-3,)4}, (58) ter/3.
From results of present analysis and also those
which agrees very closely with his numerical from Ref. [4], ignition and extinction criteria
results, where for a given droplet in a known atmosphere can
be established. Correction factors to the mass
7 = 2(a+/3)/(I +a) - 1 (59) evaporation rate due to finite activation energy
are also obtained.
is twice the ratio of the heat loss towards the
oxidizer side to the heat release at the flame.
Hence by equating Eqs. (56) and (58) an extinc- This prelect was initiated at the University of
tion DamkOhler number can be found. California at San Diego under the supervision of
The zeroth and first order mass evaporation Professor F. A. Williams, to whom the author is
rates are grateful for invaluable advice received throughout
the entire investigation. The funding in this period
Me=ln{(ct+/3)/L}, (60) was provided by the Air Force Office of Scienttfic
Research, Office of Aerospace Research, U.S. Air
and Force under Grant AFOSR- 72-2333. The work
was completed after the author ]oined his present
M 1 = 26ol/3 (1 +7) "1 lim (ill -~)' (61) affiliation. The author also wishes to thank Pro-
lessor A. Lihdn of lNTA, Madrid, Spain for
several stimulating and educational communica-
where ~ is the inner variable for expansion. tions concerning this problem.
98 C.K. LAW

References
1. Sanchez Tarifa, C., Pezez Del Notmio, P., and 6. Law, C. K., An Asymptotic Analysis on Ignition and
Ga~cia Moreno, F., Combustion of Liquid Mono- Extinction of Hydrocarbon Droplets, GMR Research
propellants and Bipropellants in Droplets, Eighth Publication 1614 (1974).
Symposium (International) on Combustion, William 7. Williams,F. A., On The Assumptions Underlying
and Wilkins, Baltimore (1962), pp. 1035-1053. Droplet Vaporization and Combustion Theories, Z
2. Peskin, R. L., and Wise, H., Ignition and Deflagration Chem. Phys, 33 (No. 1), 133-144 (1960).
of Fuel Drops, AIAA J. 4, 1646-1650 (1966). 8. Liq~n, A., personal communications.
3. Kassoy, D. R., and Williams, F. A., Effects of Chemi- 9. Williams,F. A., Combustion Theory, Addison-Wesley,
cal Kinetics on Near Equilibrium Combustion in Reading (1965).
Nonpremixed Systems, Phys, Fluids 11, 1343-1351 10. Fendeli, F. E., Ignition and Extinction on Combustion
(1968), see alsoPhys. Fluids 12, 265-267 (1969). of Initially Unmixed Reactants, J. FluM Mech. 21,
4. Linen, A., The Asymptotic Structure of Counterflow 293-303 (1965).
Diffusion Flames for Large Activation Energies, Acta 11. Lee, E. S., Quasilinearization and lnvariant Imbedding,
Astronautica 1 (No. 7-8), 1007-1039 (1974). Academic Press, New York (1968), Chap. 2.
5. Krishnamurthy, L., and Williams,F. A., Asymptotic
Theory of Diffusion Flame Extinction in the
Stagnation-Point Boundary Layer, unpublished work. Received May 21, 1974; revised October 4, 1974

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