3-6.

Bimolecular Reaction in a Liquid Film

From the problem statement,

CA = CA0
CB = 0
CC = 0

A and C
only
x=0

CA = 0
CB = CBL
CC = 0

B and C
only
x = xR

x=L

(a) The key point is that, for k , the homogeneous reaction can be treated mathematically as if it were
heterogeneous. The location of the reaction plane (x = xR ) is not known a priori.

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Conservation of A for 0 x xR :
d 2 CA
= 0; CA (0) = CA0 ,
dx 2
CA = a1 + a2 x
CA (x) =

CA0
(xR x)
xR

CA (xR ) = 0

Satises BCs.

Conservation of B for xR x L:
d 2 CB
= 0;
CB (xR ) = 0,
CB (L) = CBL
dx 2
CB = b1 + b2 x


x xR
CB (x) = CBL
Satises BCs.
L xR
To determine xR we treat the reaction plane as an interface and apply interfacial species balances. Let nI = ex
(normal to interface). In general:
Nix (xR+ ) Nix (xR ) = RSi .
Apply to A:

NAx(xR+ ) NAx (xR ) = RSA .

0

Apply to B:

NBx (xR+ ) NBx(xR ) = RSB .

0

Form the stoichiometry (A + B C), RSA = RSB = RSC . Thus,

NAx (xR ) = NBx (XR+ )
DA

dCA
dCB
(xR ) = +DB
(xR )
dx
dx
DCA0
DB CBL
=
xR
L xR
xR
DA CA0
=
L
DA CA0 + DB CBL

Notice that the reaction plane is not centered, in general. The rate of product formation is

RSC =

DA CA0
DB CBL
=
xR
L xR

For species C we have

d 2 CC
=0
dx 2
CC = C1 + C2 x
CC = C3 + C4 x

(both regions)
(0 x xR )
(xR x L).

The BCs at the edges are

CC (0) = CC (L) = 0.

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We also require CC (x) to be continuous at x = xR :
CC (xR ) = CC (xR+ ).
Satisfying these three conditions gives
CC (x) = C2 x

CC (x) = C2 xR

xL
xR L

(0 x xR )
(xR x L).

To nd the remaining constant (C2 ) we apply the interfacial balance to C:

NCx (xR+ ) NCx (xR ) = RSC
D C C2 xR
DA CA0
+ D C C2 =
xR L
xR


DA CA0 L xR
.
C2 =
DC
LxR

The concentration of C is then

CC (x) =

DA CA0
DC

CC (x) =

DA CA0
DC


L xR  x
(0 x xR )
xR
L

x
1
(xR x L).
L

In summary, the proles look like (for CBL > CA0 ),

Ci
CBL
CA (x)

CA0

CB (x)
CC (x)

xR

The concentrations are continuous at x = xR , but the concentration gradients are not. This is because there are
step changes in the uxes at the reaction plane.
(b) Length and concentration scales for reaction zone, for large (but nite) k.
The proles for A and B will look like (if CA0 > CBL ):
= thickness of reaction zone
C*A, C*B = scales there
Assume that DA ~ DB and let D = (DA + DB)/2.

Reaction zone

CA0
CBL
CA*
0
0

CB*

DA

d 2 CA
= kCA CB
dx 2

Conservation of A in reaction zone:

DCA
kCA CB
2

or

CB 2

D
.
k

(1)

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Conservation of B in reaction zone:

DCB
kCA CB
2

or

CA 2

D
.
k

(2)

(1) and (2) CA CB C .

One equation for the remaining two unknowns (C and ) comes from (1) or (2):
C 2

D
.
k

(3)

The second equation comes from overall conservation of either A or B as shown next.
Overall conservation of A:

 L
dCA 
=
kCA CB dx
DA
dx x=0
0
DCA0
DCA0
kC 2 or C 2
xR
kxR
DA CA0 L
xR =
from part (a)
DA CA0 + DB CBL
CA0 L
CA0 L

, CT = CA0 + CBL
CA0 + CBL
CT
DCT
.
C 2
kL

(4)

The same result is obtained from overall conservation of B. Solving (3) and (4) simultaneously gives
C

Da 1/3 , Da 1/3
CT
L
2

where Da kCDT L .
For Da , the reaction zone approaches a plane as assumed in part (a). The order-of-magnitude analysis
indicates how large Da must be for the result in part (a) to be accurate.

4-15. Reaction and Diffusion with a Nonuniform Catalyst Distribution

(a) Find the ux of A entering the slab for CA = CA0 at x = 0 and NAx = 0 at x = L, for Da  1.
C

Varying catalyst concentration, CC (x), gives

position-dependent rst-order rate coefcient:

CC (x)

RV A = [kCC (x)]CA

CA(x)
0

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Dimensional problem:

 x 2 
d 2 CA
DA
kCC0 1
CA = 0
dx 2
L
dCA
(L) = 0
dx

CA (0) = CA0 ,
Dimensionless (not necessarily scaled) problem:

CA
,
CA0

x
L

d 2 CA
DA CA0 d 2
=
dx 2
L2 d2

 x 2 
CA = kCC0 CA0 (1 2 )
kCC0 1
L
DA

d 2
Da(1 2 ) = 0,
d2
d 2
Da(1 2 ) = 0,
d2
d
(0) = 1,
(1) = 0
d

Da

Da

k CC0 L2
DA

kCC0 L2
DA

For Da  1 the DE is not properly scaled. That is, 1 and 1 2 1, so d 2 /d2 Da. Since
1, this
indicates that the decline in takes place over a region where
 1. In other words, there is a concentration
boundary layer.
Let Da1  1 and rescale :
X a
= X

(will need a < 0 to stretch )

a
2
d 2
2a d
=

d2
dX 2

d
d
= a
,
d
dX
2a

d 2
= 1 (1 X 2 2a )
dX 2

::::::

::

Assume dominant

2a = 1

d 2
(1 X 2 ) = 0
dx 2
(0) = 1,

a = 1/2

or

Scaled for BL

() = 0

BC changed: fast reaction gives L  char. length.

Singular perturbation expansion for BL:

= 0 (X) + 1 (X) + O( 2 )

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This form is based on the fact that appears in DE only as 1 .

No expansion is needed for the non-BL region, because = 0 there.
Substitute expansion into DE and BCs:
d 2 1
d 2 0
+
+ O( 2 ) (1 X 2 )(0 + 1 + O( 2 )) = 0
2
dX
dX 2
0 (0) + 1 (0) + O( 2 ) = 1
0 () + 1 () + O( 2 ) = 0
O(1) problem:
d 2 0
0 = 0
dX 2
0 (0) = 1, 0 () = 0
0 = eX

Same as for uniform rate const.

O() problem:
d 2 1
+ X 2 0 1 = 0
dX 2
eX
or

d 2 1
1 = X 2 eX
dX 2
1 (0) = 1 () = 0
1 = 1h + 1p

homog. particular
soln.
soln.

1h = AeX + BeX
1p = (C1 X + C2 X 2 + C3 X 3 )eX


d1p
= C1 (1 X) + C2 (2X X 2 ) + C3 (3X 2 X 3 ) eX
dX


d 2 1p
= C1 (2 + X) + C2 (2 4X + X 2 ) + C3 (6X 6X 2 + X 3 ) eX
2
dX
2C1 + 2C2 = 0
(to cancel const. terms in DE)
4C2 + 6C3 = 0

(to cancel X terms)

6C3 = 1

(to cancel X 2 terms)

(X 3 terms cancel automatically)

Solve: C1 = 1/4,

C2 = 1/4,

C3 = 1/6

1p =

0
for 1 (0) = 0

1 = AeX +

X3
X X2
+
+
4
4
6

BeX +

0
for 1 () = 0


eX

X3
X X2
+
+
4
4
6


eX

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1 =

X3
X X2
+
+
4
4
6


eX

The concentration up to O( 2 ) is then:


= eX +

X3
X X2
+
+
4
4
6


eX + O( 2 )

Compute the ux at x = 0:
dCA
(0)
dx
DA CA0 d
=
(0)
L d
DA CA0 1/2 d
=

(0)
L
dX
d

(0) = 1 + + O( 2 )
dX
4
Nx (0) = DA

Nx (0) =

(dimensional)
(original dimensionless)
(scaled dimensionless)

DA CA0 1/2

1 + O( 2 )

L
4

Flux reduction due to fall in CC in going

away from open surfacenoticeable when
BL is thick enough.

(b) Show that when the slab is reversed, the rst term in a perturbation expansion for is governed by the Airy
equation.
It is easiest to keep CC (x) the same and just reverse the BCs.

C
CC (x)

CA(x)
0

The DE is the same, so there is still a need to rescale. With the new BCs, the BL is now at x = L.
Let
Y (1 ) b

(will need b < 0)

dimensionless depth
into BL

= 1 Y b
2
d
d d 2
2b d
= b
,
=

d
dY d2
dY 2


1 2 = 1 (1 2Y b + Y 2 2b ) = 2Y b Y 2 2b

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2b



d 2
1
b
2 2b

2Y

=0
dY 2

::::::

:::::::

2b = 1 b

b = 1/3

or


d 2 
2Y Y 2 1/3 = 0
dY 2
(0) = 1,
() = 0
Powers of 1/3 should be OK for the expansion. To get the O(1) term, though, just set = 0 in the scaled eqns:
d 2 0
2Y = 0
dY 2
0 (0) = 1, 0 () = 0
To get the Airy equation, d 2 W /dz2 = zW , let
Z = cY ,
2

c = const. > 0
2

d 0
d 0
= c2
= 2Zc1 0
2
dY
dZ 2
Setting c = 21/3 gives
d 2 0
= Z0
dZ 2

(Airy eqn.)