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Abstract
A spatially smoothed jump condition is developed for the process of di!usion and reaction at a catalytic surface where a "rst-order,
irreversible reaction takes place at isolated regions on the #uid}solid interface. The point jump condition for this process is given by
!n ) D
c "kc at the c}i interface,
AG A A A
in which the rate coe$cient k undergoes abrupt changes with position on the #uid}solid interface. The averaging procedure leads to
a spatially smoothed jump condition that takes the form
!n ) D
1c 2A"k 1c 2A at the c}i interface,
AG A A A
in which the e!ective reaction rate coe$cient is determined by the solution of a closure problem. It is this e!ective reaction rate
coe$cient, times the interfacial area per unit volume, that is measured in a typical experimental study of di!usion and reaction in
a porous catalyst. The solution of the closure problem allows one to relate the intrinsic properties of the catalytic surface to k , and
the results are presented in terms of a surface e!ectiveness factor as a function of a Thiele modulus. 2000 Elsevier Science Ltd. All
rights reserved.
Keywords: Jump condition; Non-uniform boundary; Catalytic surface; Spatial averaging; E!ective reaction rate; Closure problem
0009-2509/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 1 6 1 - 5
5232 B. D. Wood et al. / Chemical Engineering Science 55 (2000) 5231}5245
HAG
R
Q
dA"
4H
R d<!
4HA
R
A
d<!
4HG
R
G
d<.
(7)
Here AH represents the area of the dividing surface
AG
illustrated in Fig. 3, while <H and <H are clearly identi-
A G
"ed in Fig. 4. To be useful, Eq. (5) requires a chemical
Fig. 2. Distribution of the reaction rate in the neighborhood of the
kinetic constitutive equation for R , and this is often
dividing surface. Q
determined by experimental observation of the average
behaviour of a catalyst.
In most catalytic processes, mass transfer occurs only
in the c-phase and the catalytic surface can be treated as
quasi-steady and reaction-controlled (Whitaker, 1986a).
For these conditions, the problem under consideration
can be simpli"ed to
*c
A #
) N "0 in the c-phase, (8a)
*t A
B.C. N ) n "!R at the c}i interface, (8b)
A AG Q
in which R can be represented in terms of the bulk
Q
concentration, c . For a "rst order, irreversible reaction
A
Fig. 3. Volume used for determination of the point jump condition. in which species A is consumed, the excess surface rate of
reaction, or the heterogeneous reaction rate, can be ex-
process of mass transfer and reaction, we express Eq. (2) pressed as
as
R "!kc . (9)
Q A
*c
A #
) N "R in the c-phase, (4a) Here we note that the rate constant, k, can be in#uenced
*t A A
by the adsorption rate constant, the desorption rate
*c constant, and a chemical kinetic rate constant. If the
G #
) N "R in the i-phase. (4b) catalytic surface is not quasi-steady and reaction con-
*t G G
trolled, one must replace Eq. (8b) with the complete form
These two equations are not valid in the interfacial region; of the jump condition and make use of an interfacial #ux
however, we will make use of both of them in that region. constitutive equation in order to determine the surface
In order to correct for the error associated with the use of concentration, c , that appears in Eq. (5). Under these
Eqs. (4a) and (4b) in the interfacial region, we need to Q
circumstances, the analysis becomes more complex
construct a jump condition (Truesdell & Toupin, 1960; (Whitaker, 1986a).
Slattery, 1990; Whitaker, 1992; Torres & Herbolzheimer,
1993) which requires that Eq. (2) be satis"ed on the
average in the volume <H illustrated in Fig. 3. The only
constraint placed on <H is that the parallel bounding
surfaces of <H lie in the homogeneous c and i-phases.
When surface transport (Ochoa-Tapia, del RmH o
& Whitaker, 1993) can be neglected, we show in Appen-
dix A that the jump condition is given by
*c
Q "N ) n #N ) n #R
*t A AG G GA Q
at the c}i interface. (5) Fig. 4. Volumes of the c- and i-phases.
5234 B. D. Wood et al. / Chemical Engineering Science 55 (2000) 5231}5245
If the concentration of species A is small compared to l and note that the theoretical development will be
A
the total concentration, the molar #ux is di!usive in restricted by
nature and can be represented by
l l , (12)
N "!D
c . (10) A A
A A A
where l represents the characteristic length for the c-
The use of this expression for the molar #ux in Eqs. (8a) A
phase illustrated in Fig. 1. If this length-scale constraint is
and (8b) leads to not satis"ed, one can form the volume average of Eqs.
*c (11a) and (11b) for the averaging volume shown in Fig.
A "
) (D
c ) in the c-phase, (11a) 1 and proceed directly to the development of a closure
*t A A
problem. The theoretical development is straightforward;
B.C. however, the numerical solution of the closure problem
would be di$cult because of the extensive grid required
!n ) D
c "kc at the c}i interface. (11b)
AG A A A to capture the e!ect of the widely dispersed catalytic sites.
This represents a pore scale description of di!usion and
reaction in a porous catalyst in which the reaction rate 3.1. Volume averaging
coe$cient, k, is a function of position.
The "rst step of the pore-scale averaging process be-
gins by locating an averaging volume at every point in
3. Spatial smoothing at the pore scale space, and one of these averaging volumes is illustrated in
Fig. 5. The size of the averaging volume V illustrated in
For most practical situations, reactions will occur at Fig. 5 must be large enough so that the non-uniformities
catalytic sites such as we have illustrated in Figs. 1 and 5. associated with the surface are spatially smoothed.
Under these circumstances, the boundary condition This generally means that r must be much, much
given by Eq. (8b) or by Eq. (11b) must be spatially larger than the distance between catalytic sites, l , and we
A
smoothed in order to produce a useful pore scale descrip- express this idea by the constraint
tion of the process. This spatially smoothed jump condi-
r l . (13)
tion will contain information about the distribution of A
catalytic sites illustrated in Fig. 5 and information about In terms of the averaging volume, V, the average of Eq.
the intrinsic reaction rate coe$cient associated with (2) is given by
those sites. A key assumption inherent in the theoretical
analysis is that the distance between the metal clusters is 1 *c 1 1
d<#
) N d<" R d<. (14)
small compared to the pore diameter. Under these cir- V V *t V V
V V
cumstances, the disparate length scales will allow us to
perform the averaging procedure at two di!erent length Use of the general transport theorem and the spatial
scales in exactly the way that hierarchical systems are averaging theorem leads to
treated (Cushman, 1990; Quintard & Whitaker, 1996).
We designate the distance between catalytic sites as * 1 1
c d< #
) N d<
*t V V
V V
1
" R d< . (15)
V V
1
1t 2" t d<, (16)
V V
*1c 2
#
) 1N 2"1R 2 everywhere. (17)
*t
regions of the c and i-phases. For those averaging vol- process. To be explicit, we note that 1R 2 is dexned by
Q
umes, Eq. (17) provides the following two transport equa-
tions:
*1c 2A
HH
AG
1R 2 dA"
Q 4HH
1R 2 d<!
4HH
A
1R 2A d<
A
A #
) 1N 2A"1R 2A in the c-phase,
(18a)
*t A A ! 1R 2G d<, (21)
HH G
4 G
*1c 2G
G #
) 1N 2G"1R 2G in the i-phase, (18b) where <HH and AHH are illustrated in Fig. 7. The parallel,
*t G A AG
bounding surfaces of <HH must lie in regions of the c- and
in which the intrinsic averages are de"ned by the i-phases that are homogeneous with respect to vol-
ume-averaged quantities, and this is indicated in Fig. 7,
1 1 where d represents the thickness of the interfacial region
1t 2A" t d<, 1t 2G" t d<.
A < A G < G and r represents the radius of the averaging volume, V.
A 4A G 4G
For the typical porous catalyst, our governing di!eren-
(19)
tial equations and boundary condition given by Eqs.
(18a), (18b) and (20) reduce to
3.2. The jump condition Spatially smoothed equations for diwusion and reaction
in a catalyst:
Eqs. (17), (18a) and (18b) are completely analogous to
Eqs. (2), (4a) and (4b), thus by following an analysis *(c )A
A #
) (N )A"0 in the c-phase, (22a)
similar to that presented in Appendix A we can immedi- *t A
ately develop a jump condition analogous to Eq. (5).
B.C.
*1c 2
B.C. Q "1N 2A ) n #1N 2G ) n #1R 2 1N 2A ) n "!1R 2 at the c}i interface (22b)
*t A AG G GA Q A AG Q
and these equations should be thought of as the spatially
at the c}i interface. (20)
smoothed pore-scale equations describing di!usion and
Eqs. (18a), (18b) and (20) form a complete description of reaction in a porous catalyst. When these equations are
the transport and reaction in the porous catalyst where averaged over the volume illustrated in Fig. 1, one ob-
the heterogeneous surface reaction has been spatially tains the classic di!usion}reaction equation that can be
smoothed. Here one must remember that Eqs. (18a) and used with experimental data to determine 1R 2 times
Q
(18b) are not valid in the interfacial region; however, they the surface area per unit volume.
will be used in that region in conjunction with the jump
condition given by Eq. (20). The jump condition has been
constructed on the basis that Eq. (17) is satis"ed on the 4. Relation between 1R 2 and R
Q Q
average in the interfacial region. The surface excess
quantities 1c 2 and 1R 2 that appear in Eq. (20) are In addition to obtaining measured values of 1R 2 , it
Q Q Q
de"ned in a manner analogous to the point quantities, is important to relate this quantity to the point value, R ,
Q
c and R , appearing in Eq. (5) (see Appendix A) except since this allows one to determine the e!ect of the distri-
Q Q
for the change of scale that accompanies the averaging bution of the catalytic sites on the measured reaction
5236 B. D. Wood et al. / Chemical Engineering Science 55 (2000) 5231}5245
HAG
R dA" R d<.
Q
4H
(23)
HH
AG
1R 2 dA" 1R 2 d<.
Q
4H
(24)
1
1R 2"x " R "x y d<. (25)
V(x) >
Vx
1
1R 2 dA" R "x y d< d<. (26) given by
Q V(x) >
HH
AG 4HH Vx
V(x)"pr (28)
However, we need the relation between 1R 2 and R ,
Q Q
and in order to develop this relation with a minimum of and we can use this representation to express Eq. (27) as
e!ort we will ignore all e!ects of curvature so that Eq.
(26) can be expressed as 1 X>D Fp PP EX>(P \P
1R 2 "
Q 4/3pr
X>D 1 X\D F P EX\(P \P
1R 2 " R "x y d< dz. (27)
Q V(x) >
X\D
Vx
;R dg r dr dh dz, (29)
Here we have chosen <HH to be a right circular cylinder
having a vanishingly small cross-sectional area, AHH, and
AG in which z is the distance measured from the dividing
we have represented the normal direction as the z-direc-
tion. The graphical representation of Eq. (27) is shown in surface to the centroid of the averaging volume. In this
Fig. 9 where the distance D is large enough so that the form of Eq. (27) it is understood that 1R 2 is associated
Q
with the position x and that R is a function of r, h and
averaging procedure is carried into the homogeneous re-
gions of the c- and i-phases. Neglecting the e!ects of z. We can immediately interchange the order of integra-
curvature means that d is small compared to the radius of tion in Eq. (29) to express the average rate of heterogen-
curvature, and it also means that the radius associated eous reaction as
with V(x) is small compared to the radius of curvature.
This is the type of situation that we have illustrated in 1 Fp PP X>D EX>(P \P
1R 2 "
Fig. 5. Q 4/3pr
F P X\D EX\(P \P
X>B
R " R dz (31)
Q
X\B
and it is this integral that we must locate within Eq. (30) if
we are to relate 1R 2 to R . Locating this particular
Q Q
integral in the representation for 1R 2 requires that the
Q
order of integration in Eq. (30) be changed.
In order to interchange the order of integration in the
last two integrals in Eq. (30), we "rst identify the domain
of integration as indicated in Fig. 10 where we have
simpli"ed the nomenclature by using the function a de-
"ned by
Fig. 12. (a) Domain of integration for non-zero values of R . (b)
a(r)"(r !r, 0)a)r . (32) Transformed domain of integration for non-zero values of R .
integrals contained in Eq. (30), and this domain is illus- X>D EX>? E>? X>B
R dg dz" R dz dg. (35)
trated in Fig. 11.
The limits of integration for the interfacial region are X\D EX\? E\? X\B
given in more detail in Fig. 12a, and on the basis of these Use of the de"nition of the surface excess rate of reac-
limits we can express the last two integrals in Eq. (30) tion given by Eq. (31) allows us to express Eq. (35) in the
according to form
X>D EX>? EB\? XE>?
R dg dz " R dz dg X>D EX>? E>?
R dg dz" R dg"2a(r)R . (36)
X\D EX\? E\B\? X\B Q Q
X\D EX\? E\?
E\B>? XB Substitution of this result into Eq. (30) and making use of
# R dz dg
the de"nition of a given by Eq. (32) leads to
EB\? X\B
EB>? XB 1 Fp PP
# R dz dg. (34) 1R 2 " (2(r !r)R r dr dh. (37)
Q 4/3pr Q
E\B>? XE\? F P
5238 B. D. Wood et al. / Chemical Engineering Science 55 (2000) 5231}5245
1 Fp PP
1R 2 " w(r)R r dr dh, (39)
Q pr Q B.C.
F P
in which the weighting function is given by !1D
c 2A ) n "1kc 2
A A AG A AG
w(r)"(1!(r/r ). (40) at the c}i interface. (45b)
The area average of the weighting function is one, i.e., At this point it is important to remember that 1c 2A and
A
1N 2A are de"ned in terms of the averaging volume
A
1 Fp PP illustrated in Fig. 6. For averages de"ned in the homo-
w(r)r dr dh"1 (41)
pr geneous c-phase, we have
F P
and if R is uncorrelated with the radial position we can
Q 1D
c 2A"D
1c 2A (46)
A A A A
approximate Eq. (39) by
and this allows us to express Eqs. (45a) and (45b) as
1 Fp PP
1R 2 " R r dr dh. (42) *1c 2A
Q pr Q A "
) (D
1c 2A) in the c-phase, (47a)
F P *t A A
We can also express this result as
B.C.
1
1R 2 " R dA"1R 2 , (43) !n ) D
1c 2A"1kc 2
Q A Q Q AG AG A A A AG
AG AG
in which A represents the area of the c}i interface at the c}i interface. (47b)
AG
occupied by the spherical averaging volume illustrated in
To develop the closure problem, we make use of the
Fig. 9 when the centroid of the averaging volume is
decomposition given by
located on the interface.
While Eq. (43) has great intuitive appeal, one must c "1c 2A#c (48)
remember that the e!ects of curvature have been ignored A A A
and we have assumed that R is not correlated with the and subtract the averaged equations from the point
Q
radial distance from the centroid of the averaging vol- equations to obtain
ume. This latter simpli"cation is entirely consistent with
*c
the restriction given by Eq. (13). A "
) (D
c ) in the c-phase, (49a)
*t A A
B.C.
5. Closure problem
!n ) D
c "kc !1kc 2
AG A A A A AG
Eq. (43) provides us with a relation between the point
value and the averaged value of the reaction rate. How- at the c}i interface. (49b)
ever, in order to explicitly develop the jump condition of
We now decompose the reaction rate coe$cient in
the form of Eq. (1) we must develop a relation between
terms of an area average and a spatial deviation
the e!ective reaction rate parameter and the point-scale
processes. This is accomplished by the development of k"1k2 #kI (50)
a closure problem. To begin, we return to the pore scale AG
description of the di!usion and reaction process given by and make use of the decomposition given by Eq. (48) to
Eqs. (11a) and (11b) which we repeat here as obtain the following form of Eqs. (49a) and (49b)
*c *c
A "
) (D
c ) in the c-phase, (44a) A "
) (D
c ) in the c-phase, (51a)
*t A A *t A A
B. D. Wood et al. / Chemical Engineering Science 55 (2000) 5231}5245 5239
!n ) D
c "kc !1kI c 2
s "0, (55a)
AG A A A A AG A
#k 1c 2A at the c}i interface. (51b) B.C. 1
GHI A
!n ) D
s !ks #1kI s 2 "kI at A , (55b)
AG A A A A AG AG
Here we have used the simpli"cation indicated by B.C. 2 s "0, z"h. (55c)
A
11c 2A2 "1c 2A (52) Periodicity: s (r#l )"s (r), i"1, 2, 3. (55d)
A AG A A G A
and the length-scale constraints associated with this ap- Average: 1s 2A"0. (55e)
A
proximation are discussed elsewhere (Whitaker, 1999,
Chapter 1). We only need to solve Eqs. (51a) and (51b) in Here we have imposed the condition that the average of
some representative region associated with the catalytic the closure variable is zero, and this is necessary in order
surface, and such a region is illustrated in Fig. 13. In that to evaluate the area integral represented by 1kI s 2 .
A AG
region, we can ignore variations in the molecular di!us- Closure problems of this type are described by Quintard
ivity and we can treat the process as quasi-steady and Whitaker (1993,1995) and by Whitaker (1999, Chap-
(Whitaker, 1999, Chapter 1) so that the closure problem ter 2).
becomes
5.1. Closed form
c "0, (53a)
A
B.C. 1 Our objective in this study is to develop a representa-
tion for 1kc 2 that can be used with Eqs. (47a) and
A AG
!n ) D
c "kc !1kI c 2 (47b) in order to determine 1c 2A. On the basis of the
AG A A A A AG A
decomposition given by Eq. (48), and the representation
#k 1c 2A at the c}i interface, (53b) given by Eq. (54), we obtain
GHIA
1kc 2 "1k(1#s )2 1c 2A.
A AG A AG A
(56)
B.C. 2 c "0, z"h. (53c)
A The decomposition represented by Eq. (50) can be used
Periodicity: c (r#l )"c (r), i"1,2,3. (53d) to express this result in the form
A G A
1kc 2 "(1k2 #1kI s 2 )1c 2A. (57)
Here we have treated the region shown in Fig. 13 as A AG AG A AG A
a spatially periodic model of a non-uniform catalytic
This suggests that we de"ne an e!ective reaction rate
surface. The boundary condition imposed at z"h is
coe$cient according to
based on the idea that the di!erence between c and
A
1c 2A is caused by the heterogeneous chemical reaction k "1k2 #1kI s 2 ,
A CDD AG A AG
(58)
at the c}i interface. This means that c will be zero at
A
some distance, h, from the catalytic surface and this so that our di!usion and reaction process can be de-
distance must be determined by trial and error; however, scribed by
for a di!usive process we know that h will be on the order
of, or less than, l . The reaction rate coe$cient, k, can be *1c 2A
A A "
) (D
1c 2A) in the c-phase, (59a)
an arbitrary function of position on the surface; however, *t A A
5240 B. D. Wood et al. / Chemical Engineering Science 55 (2000) 5231}5245
d
d thickness of the interfacial region, m c d<# N ) n dA" R d<. (A.5)
dt
u (1k2 l/d D , Thiele modulus 4H H 4H
AG A N A
The volume <H can be expressed in terms of the volumes
of the c and i-phases according to
Acknowledgements <H"<H#<H, (A.6)
A G
while the surface area of <H can be expressed in terms of
Support for BW and SW was provided by the
the external portions of the bounding surfaces of the
ECRILDRD program at Paci"c Northwest National
c and i-phases to obtain
Laboratory. Paci"c Northwest National Laboratory is
operated for the DOE by Battelle Memorial Institute AH"AH#AH. (A.7)
A G
under contract DE-AC06-76RLO 1830. Integration of Eq. (A.2) leads to a variation of Eq. (A.5)
that contains the interfacial area as indicated by
d
Appendix A. Derivation of the jump conditions c d<# N ) n dA# N ) n dA
dt A A A A AG
4HA HA HAG
In order to develop the point jump condition at the c}i
interface shown in Fig. 1, we begin with the continuity
equation for species A that is valid everywhere and we
"
4HA
R d<
A
(A.8)
express this equation as and the analogous result for Eq. (A.3) has the form
d
*c c d<#
G
N ) n dA#
G G
N
G
) n dA
GA
#
) N "R everywhere. (A.1) dt
*t 4HG HG HGA
the c-phase we determine the concentration of species Here we have used n to represent the unit normal
GA
A by means of the special form of Eq. (A.1) given by vector directed from the i-phase toward the c-phase, and
we have made use of the convention that
*c
A #
) N "R in the c-phase. (A.2) n "!n ,
GA AG
AH "AH .
GA AG
(A.10)
*t A A
The unit normal vectors, n , n and n are illustrated in
GA A G
By in the c-phase we mean everywhere in the c-phase Fig. 15.
including the interfacial region where Eq. (A.2) is not Our objective in the development of a jump condition
valid. We treat the i-phase in the same manner and is to satisfy the macroscopic equation represented by Eq.
express the governing di!erential equation as (A.5) and not the point equation given by Eq. (A.1). The
procedure consists of solving the point equations given
*c by Eqs. (A.2) and (A.3) subject to the appropriate jump
G #
) N "R in the i-phase. (A.3)
*t G G condition. To accomplish this, we "rst subtract Eqs. (A.8)
and (A.9) from Eq. (A.5) and arrange the result in the
The jump condition at the c}i interface will be construc- form
ted so that Eqs. (A.2) and (A.3) will provide a concentra- d
tion "eld that satis"es Eq. (A.1) on the average in the c d<! c d<! c d<
dt A G
volume <H illustrated in Fig. 3. We can form the integral 4H 4HA 4HG
of Eq. (A.1) over <H to obtain
# N ) n dA! N ) n dA
A A
H HA
*c
d<#
) N d<" R d<. (A.4)
H *t N ) n dA
4 4H 4H !
G G
HG
Since the limits of integration associated with <H do not
depend on time, we can use the general transport the- ! (N !N ) ) n dA
H A G AG
orem to interchange di!erentiation and integration in AG
*c
Q #
) N "(N !N ) ) n #R
*t Q Q A G AG Q
N ) n "!R at the c}i interface. (A.19)
N ) n dp" N ) n dA! N ) n dA A AG Q
H Q Q H A A
! HA and when species A is consumed by a "rst order, irrevers-
ible heterogeneous reaction we have
! N ) n dA. (A.13)
G G
HG N ) n "kc at the c}i interface (A.20)
A AG A
Excess surface rate of reaction:
This is Eq. (7b) in the main body of the paper.
H
AG
R dA"
Q 4 H
R d<!
4H
A
R
A
d<
A.1. Volume-averaged jump condition
!
4 H
G
R d<.
G
(A.14) Given Eq. (A.1) we can form the volume average to
obtain
The use of these three de"nitions in Eq. (A.11) leads to an
integral surface transport equation of the form 1 *c 1 1
d<#
) N d<" R d< (A.21)
V V *t V V
V V
d
c dA# N ) n dp
dt Q Q Q and use of the general transport theorem and the spatial
HAG !H
averaging theorem leads to
"
(N !N ) ) n dA#
A G AG R dA.
Q
(A.15)
HAG HAG * 1 1
c d< #
) N d<
*t V V
V V
The surface transport theorem and the surface divergence
theorem (Ochoa-Tapia et al., 1993) can be used to express
this result in the form 1
" R d< . (A.22)
V V
*c
Q dA#
) N dA
H *t Q Q Use of the traditional nomenclature given by
AG HAG
1
" (N !N ) ) n dA# R dA (A.16) 1t 2" t d<, (A.23)
H A G AG H Q V
AG AG
V
5244 B. D. Wood et al. / Chemical Engineering Science 55 (2000) 5231}5245
allows us to express Eq. (A.22) as than the radius of curvature of the surface, and when this
is not the case we encounter di$culties as indicated in
*1c 2 Fig. 17. There we have shown an interface for which the
#
) 1N 2"1R 2 everywhere. (A.24)
*t thickness of the interfacial region is larger than the local
radius of curvature. The volume <H illustrated in Fig. 17
From here one needs only to repeat the analysis from Eq. has been constructed using lines perpendicular to the c}i
(A.1) to Eq. (A.19) to obtain the volume-averaged jump interface; however, that volume does not include the
condition given by homogeneous i-phase. Other volumes can be chosen
that will include the homogeneous regions in both the
1N 2A ) n "!1R 2 at the c}i interface. (A.25) c and i-phases; however, they will not permit arbitrary
A AG Q
values of AH thus we are prevented from extracting Eq.
This is Eq. (21b) in the main body of the paper. AG
(A.17) from Eq. (A.16). At this point of time, it is not clear
how to resolve this di$culty; however, it is clear that our
analysis is restricted to cases in which the mean radius of
Appendix B. E4ect of curvature curvature of the surface is large compared to the thick-
ness of the interfacial region. For the jump condition
In this appendix we examine the simplest case of a cur- given by Eq. (A.19), this thickness is d and it will often be
ved surface, i.e., the surface of a sphere. A two-dimen- small compared to the mean radius of curvature of the
sional representation of this surface is given in Fig. 16 surface. On the other hand, the thickness of the interfacial
where we have shown several possibilities for the volume region associated with the jump condition given by Eq.
<H. In this case it is clear that the limits of integration (A.25) is 2r #d and the restriction that this be small
associated with Eq. (A.16) are arbitrary and we encounter compared to the mean radius of curvature will be more
no di$culty in passing from Eq. (A.16) to Eq. (A.17). In di$cult to satisfy.
Fig. 16 the thickness of the interfacial region is smaller
B.1. Inyuence of the curvature on the heterogeneous rate of
reaction
HAG
R
Q
dA"
4H
R d<.
(B.1)
P
R (4pR )" R 4pr dr. (B.2)
Q
P0
As an example, we take the rate of reaction to be given by
according to
K K
1#6(d/R ) exp(!3m)m dm#3(d/R ) exp(!3m)m dm
R "R d/3 K K . (B.5)
Q GFFFFFFFFFFFFFHFFFFFFFFFFFFFI
When the thickness of the interfacial region is small Mukesh, D., Morton, W., Kennedy, C. N., & Cutlip, M. B. (1984b).
compared to the radius of curvature of the interface, Eq. Island models and the catalytic oxidation of carbon monoxide and
carbon monoxide-ole"n mixtures. Surface Science, 138, 237}257.
(B.5) reduces to the expected result that the heterogen- Northrup, S. H. (1988). Di!usion-controlled ligand binding to multiple
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curvature. 5847}5850.
Ochoa-Tapia, J. A., del RmH o, P. J. A., & Whitaker, S. (1993). Bulk
R "R d/3, dR . (B.6)
Q and surface di!usion in porous media: An application of the sur-
face averaging theorem. Chemical Engineering Science, 48,
It is important to remember that the thickness of the 2061}2082.
interfacial region associated with the average heterogen- Quintard, M., & Whitaker, S. (1993). One- and two-equation models
eous rate of reaction, 1R 2 , is not d but the larger value for transient di!usion processes in two-phase systems. In Ad-
Q
represented by 2r #d. Under these circumstances, we vances in heat transfer, vol. 23 (pp. 369}465). New York: Academic
except 1R 2 to be independent of the curvature when Press.
Q Quintard, M., & Whitaker, S. (1995). Local thermal equilibrium for
2r #dR .
transient heat conduction: Theory and comparison with numerical
experiments. International Journal of Heat and Mass Transfer, 38,
2779}2796.
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