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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.
22
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:
Apply to B:
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
(both regions)
(0 x xR )
(xR x L).
23
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).
DA CA0
DC
CC (x) =
DA CA0
DC
L xR x
(0 x xR )
xR
L
x
1
(xR x L).
L
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
DCA
kCA CB
2
or
CB 2
D
.
k
(1)
24
or
CA 2
D
.
k
(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.
CC (x)
RV A = [kCC (x)]CA
CA(x)
0
71
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
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
72
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
6C3 = 1
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
73
1 =
X3
X X2
+
+
4
4
6
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
(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
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.)