Chemical Engineering S&me. 1952, Vol. 10, pp. 281 to 284. Pergsmon Press Ltd.

d. London Printed in Great Britain

A note on the (‘ Danckwerts ” boundary conditions for continuous flow

reactors
J. R. A. PEARSON

Imperial Chemical Industries Ltd., Akers Research Laboratories, The Frythe, Welwyn, Herts.

Abstract-A mathematical justification is given for the use of the “ Danckwerts ” boundary
conditions for continuous flow reactors. It is shown that the apparent indeterminacy, which
DANCE~ERTS resolves intuitively, is caused by the use of a discontinuous coefficient of diffusion.
By treating this as the limit of a cont~uous fusion and imposing eont~uity of the reactant
concentration as the physically relevant boundary condition, the Danekwerts solution is obtained
in the limit.

RBsum&--L’auteur donne une justification mathematiques des conditions aux limites utilisees
par DANCKWERTS dans le cas d’un reaeteur a Bcoulementcontinu. I1 montre que l’indt’termination
apparente resolue ~t~tivement par D~~cxwmzrs est inherente it un coefficient de fusion
discontinu. I1 con&d&e ce coefficient comme la limite d’une fonction continue et il impose une
continuite a la concentration du reactant comme &ant la condition limite physiquement correcte :
la solution de DANCKWERTSest alors obtenue a la limite,

Zusammenfassnng-Die G~~be~n~ngen nach DANCKWERTS fur den kon~uierlich durch-

str6mten Reaktor werden mathematisch gerechtfertigt. Die anscheinende Unbestimmtheit, die
DANCKWERTS intuitiv aufltist, ist durch die Verwendung eines diskontinuierlichen Diffusions-
koeffizienten verursacht. Bebandelt man diesen als Grenzfall einer kontinuierlichen Funktion
und setzt die Stetigkeit der Konzentration des Reaktanten als die physikalisch entscheidende
Grenzbedingung fest, so erhalt man die DANCKWERTS-L~SIJNC im Grenzfall.

1. INTRODUCTION y = 0, where the diffusion coefficient discon-

IN an oft-quoted paper (Chem. Etgng. Sci. I953 2 tinuously changes from zero, is obtained by a
I),DANCKWERTS has considered the steady state consideration of mass balance, and is
ffow of r&&ant through a packed tubular reaction dc
vessel in terms of a second order ordinary differen- UC* = w: - D .
qj” Y = 0, (2)
tial equation (equation 30 in Eoc. cit.). This
equation for the steady state concentration, c, where c* is the concentration in the entering
of reactant in a first order reaction supposes that stream.
c is a function of one space variable only, y, the A similar relation is obtained for c at the exit
distance down the tube. The streaming velocity, from the tube, y = L, tihere D again changes
21, the rate constant, k, and the (constant) coeffi- discontinuously, but is replaced by DAMXWERTS,
cient of ~sion, 23, enter as parameters into on intuitive grounds, by the stronger condition
the diffusion equation, which may thus be written
-de = 0, y = L.
= 0-t. (1)
dY
Conditions (2) and (3) lead to a unique solution
The boundary condition at the entry to the tube, for c ; however this solution, as presented in

t D~~c~vvnnrs’ notation is retained for ease of comparison.

231
 J. R. A. PEARSON

DANCKWERTS’ paper, appears to rely for its where D, and A > 1 are constants. This is
uniqueness on the acceptance of an intuitive shown diagrammatically in Fig. 1. The diffusion
boundary condition. If only because this boun-
dary condition has not been universally accepted,
it seems desirable to investigate a little more
closely the formal. mathematical implications of
the idealization represented by equation (1) and
the boundary conditions (2) and (3).
First of all, we observe that in the general
solution to (l), using boundary condition (2) at
y = 0 and a similar condition at y = L, a discon-
V I I
L-I/A
\
L
0 ‘/A
tinuity in c, at either y = 0 or y = L, or both, is Y-
necessarily consequent upon the imposed discon- FIG. 1. Coefficient of diffusion, D, as a function of yS
tinuities in D. Within the reactor, i.e. where
0 < y < L, we naturally consider only continuous
solutions for c. This we do for sound physical equation which, for a non-constant coefficient of
reasons, but not for mathematical ones, for it diffusion, must be written
may easily be verified that solutions exist for c
that are discontinuous within the region 0 < y < L. _u.!%hc=O, (5)
This suggests, as a next step, that we should dY
eliminate, if possible, the discontinuity in D, and becomes, in the three regions (i), (ii) and (iii),
seek solutions for c that are continuous everphere,
and are therefore physically acceptable. We may (i) y.~+(1-&)~--& c1 = 0, (6.i)
do this in a variety of ways. In the following 0 0

section, we shall deliberately choose a form for

(ii) '2 _ g - E$ - $ c2 = 0, (6.ii)
D, the diffusion coefficient, which is continuous
everywhere and which, by means of an obvious
limiting process, may be made to approach as (iii) z.~-+il+&~-&oca=O, (&iii)
closely as we please to the “ top hat ” distribution
of DANCKWERTS. It will be shown that a unique where we have written z=L-y, (7)
solution for c is in fact obtained without resort
and ci, ca and ca refer to the solution for c within
to intuition, and that this solution tends, in the
the three regions. The boundary conditions that
limit, to the solution obtained by DANCKWERTS.
we must apply to this set of three equations are
In other words the apparently intuitive boundary
condition (3) becomes the inevitable result of the
limiting process applied to the continuous
solution.
Cl = c* at y = 0,
1
dc dc
c2 = cl, -2 = -1 at y = l/A,
dY. dY
. (8)
2. MATHEMATICALTREATMENT
c&. = c2,
h2
- = -
h-dz aty=L
We replace the constant coefficient of diffusion dY
used by DANCKWERTSby the continuous form -(l/A), (s = l/A),
(i) D=AD,y when 0 < y < l/A (4.i) since mass balance at y = l/A and at y = L - l/A
requires that ok/dy as well as c be continuous
(ii) D = D, when l/A <y <L -
there. We have specified two boundary condi-
- (l/A) (4.ii)
tions for ca and c2, but only one for c,. Thus, at
(iii) D = AD, (L - y) when L -(l/A) first sight, the system is apparently indeter-
< y <L (4.iii) minate.

232
 A note on the “ Danckwerts ” boundary conditions for continuous flow rcactow

We now consider the general solution for each cp = do (1 + (k/AD, + U) z + 0 (z”) . . . .) (14)
of the three equations (6). That for (6.ii) can be
written directly as that is bounded in the region (iii).

e2=e,,exp[~(l+1/1+u~kDo)]+ At z = 0, cs(]) = d,.

At z = l/A, cQ(l) = do + o (l/P),

+ c22exp [g (1-J’]],
csl and cza being arbitrary constants. This
involves two linearly independent solutions which
are finite in the region (ii). Those for (Si) and
(6iii) are best considered in terms of ascending
power series expansions about the points y = 6
and z = 0. (It will be sufficient to do this because
we will later apply the limiting process A -t co).
Thus, if we write
c1 = y’ (a, + a, y + . . . . . . + anyn + . . . . . (10)
and substitute into equation [6(i)] we find that
r = 0 or go,
tg)
y = (kd,/AD, + u) + 0 (l//P).
We now see that the five boundary conditions
(8) are in fact sufficient to define a unique solu-
tion for c, in terms of c*, since there are only
five constants, cal, cp2 [from (2)1, a0 [from (ll)],
b, [from (12)] and do [from (l4)] to be determined.
We need not evaluate explicitly these constants
in terms of c*, but proceed at once to the limit
A + oo. This corresponds, in the limit, to the
discontinuous form for D chosen by Danckwerts.
As l/A -+ 0, we see that
c1(l) (l/A) -+ c1(‘) (0),

giving the two linearly independent solutions cJ2) (l/A) + b, while cl(‘) (0) = 0. In
but that
other words the solution c1c2) represents, in the
c1(1) = a, [l + (k/AD, - U) y + 0 (y/“) . . . . *.] (11)
limit, a discontinuity in c. Thus (2) is the correct
and cl(*) = b, y@lAD*) [l + (k/AD, + U) y + limiting boundary condition. Similarly, as
+ 0 (Y2) *---1 (12) l/A +O,
cat’)(l/A) -+ c&l)(0)
that are bounded within the region (i).

At y = 0, c$) = a 0, c1(‘) = 0. while dc,(‘)

dz (l/A) + 0. Thus the strong boundary

At y = l/A, cl(l) = a, + 0 (l/A*), condition (3), implying continuity of c at y = L.

is recovered.
cp = b, (l/A) WAD,) + 0 (l/A),
3. DISCUSSION
= A2_ u
dCl(”
+ 0 WA2)1
dy It might be argued that the choice (Pi), (4ii) and
(4iii) for D is in some sense particular, and that
Sf2’= b, * ; (l/A)@‘An”) + 0 (l/A), a different limiting solution would be obtained by
0
using a different continuous distribution for D
since l/A is small. within the regions (i) and (iii). This is not so, and
the same limiting solution can in fact be demon-
Similarly if we write
strated for a very wide class of functions D.
cs = 7! (do + a, z + . . . . . . d,z” + . . . ), (13) What we have done in section 2 is to give but an
illustrative example of the effect of the sign of
and substitute into equation (biii) we find that
u on solutions for c in equation (5) in the neigh-
bourhood of points where D becomes equal to
s=O or -so,
zero. This purely mathematical dependence on the
giving only one solution sign of u can be interpreted physically, as

283
 J. R. A.
DANCKWERTS has done, in terms of different
boundary conditions to be applied at the entry
to or at the exit from a packed tubular reactor,
where the diffusion coefficient changes rapidly
from zero.
The same procedure can be adopted to obtain
relevant boundary conditions in more complicated
situations involving diffusion where there are
several reactants, and where temperature varies.
It can readily be shown that the boundary con-
284
PEARSON
dition (a), which implies continuity of the
variables at the exit, is recovered in every case.
It need hardly be pointed out that the use of a
discontinuous diffusion coefficient so simplifies
the solution of the diffusion equation that it
enables analytical results to be obtained in many
cases where a more physically acceptable form
for D would make exact solution impossible. To
this extent, the justification given above becomes
of practical value.