Chapter 18.

Concentration distributions p
in solids and in laminar flow
Shell mass balances, boundary conditions
Diffusion through a stagnant film Diffusion through a stagnant film
Diffusion with heterogeneous and
homogeneous chemical reaction homogeneous chemical reaction
Diffusion into a falling liquid film (gas
absorption, solid dissolution)
Diffusion and chemical reaction inside a
porous catalyst
Diffusion in a three-component gas system
1
Diffusion in a three-component gas system
C t ti di t ib ti i lid d Concentration distributions in solids and
in laminar flow
Flux N
A
: moles of A per unit area per unit
time (system fixed in space)
c
( ) N N x
z
x
cD N
Bz Az A
A
AB A
+ +
c
c
=
flux flux flux
convective molecular combined
flux flux flux
2 A relationship between N
A
and N
B
is needed.
Chemical reaction
Reaction rate: chemical reaction constant
Homogeneous reaction Heterogeneous reaction
c k R
n
A
' ' '
A
=
c k N
surface
n
A
' '
surface
A
=
balance mass the
in included is It
diti b d
a as included is It
balance mass the
condition boundary
3
18.1 Shell mass balances
Balance
d ti f t
(
0
ogeneous hom
by A of mass of
production of rate
of mass
of rate
of mass
of rate
=
(
(
(

+
(
(

(
(

reaction
ogeneous hom
out A in A
(
(

(
(

(
(

4
B d diti Boundary conditions
Specified concentration at a surface
Specified mass flux at a surface
At the surface: At the surface:
( )
b
c c k N =
Ch i l ti t th f
( )
Ab 0 A c 0 A
c c k N =
Chemical reaction at the surface
5
18.2 Diffusion Through g
a stagnant gas film
Liquid A is evaporating
into gas B into gas B.
Constant level for liquid A
A stream of gas mixture A
and B flows slowly on the y
top.
A and B are ideal gases A and B are ideal gases
Plug flow
6
Concentration profiles p
x equilibrium x
A1
equilibrium
concentration at
i t f
vap
interface
p
p
vap
A
B d di i Boundary conditions
BC1 and BC2
1 A A 1
x x z z at
x x z z at
= =
= =
7
2 A A 2
x x z z at = =
E ti Equations
B is stationary
( )
Bz Az A
A
AB Az
N N x
z
x
cD N + +
c
c
=
Using N
Bz
=0
z c
x cD
N
A AB
c
z
x
x 1
cD
N
A
A
AB
Az
c
c

=
Mass balance
0 N S N S
z z
Az
z
Az
=
A +
8
z z z A +
Equations
Taking limit when
0
dN
Az
=
0 x A
0
dz
=
Introducing N
az
0
dx cD d
A AB
= |
|

|
0
dz x 1 dz
A
|
.

\

9
Equations Equations
i Integrating
1
A
A
AB
C
dz
dx
x 1
cD
=

Integrating, again
A
dz x 1
C C ) 1 l ( +
(no concentration as
boundary condition)
2 1 A
C z C ) x 1 ln( + =
Using BCs 1 and 2
| | z z
|
.
|

\
|

|
.
|

\
|
= |
.
|

\
| 1 2
1
z z
z z
2 A A
1
x 1
1
x 1
10
. \

. \

1 A 1 A
x 1 x 1
Other calculations Other calculations
For x
B
A B
x 1 x =
Avg. conc.
f B i th
1
2 B
z
B
x
dz
x
2
|
|

|
,
}
of B in the
tube
2 B
1 B
2 B
z
z
1 B
1 B
avg , B
x
ln
x
x
x
x
2
1
|
|

|
|
.
|

\
|
= =
}
}
0
1 B
2 B
z
1 B
x
ln
dz
x
1
|
.
|

\
|
}
Rewriting
z
1
( )
1 B 2 B
avg B
l
x x
x

=
11
( )
1 B 2 B
avg , B
x x ln
R t f t f t th li id Rate of mass transfer at the liquid-gas
interface
Rate of
evaporation
z z
B
1 B
AB
z z
A
1 A
AB
z z
Az
dz
dx
x
cD
dz
dx
x 1
cD
N
1 1
1
+ =

=
= =
=
( )
AB 2 B AB
z z 1 B z z 1 A
cD x
l
cD
1 1
|
|

|
= =
( )( )
( )
2 A 1 A
ln
B 1 2
AB
1 B
2 B
1 2
AB
z z
Az
x x
x z z
cD
x
x
ln
z z
cD
N
1

= |
.
|

\
|

=
=
12
Experimental determination of
Diff i i i
Film model for mass
Diffusivities
Film model for mass
transfer
N h f i Near the surface is a
slowly moving film
Substance A diffuses
through this film
Sharp transition from
stagnant film to a well- g
mixed fluid
Concentration gradient
13
Concentration gradient
only in the film (linear)
18.5 Diffusion into a falling liquid film
(gas absorption)
d i Forced convection mass
transfer
Absorption of gas A by
a laminar film liquid B q
A slightly soluble in B
S ll t ti Small penetration
distance compared with
fil thi k film thickness
Ex. Absorption of
14
Oxygen in water
Equations qu o s
Velocity profile (
| |
2
x
Velocity profile
(

|
.
|

\
|
o
=
max z
x
1 v ) x ( v
C varies with x and z Mass balance over a

. \
C
A
varies with x and z. Mass balance over a
element of volume (Ax Az W)
x W N x W N
z z
Az
z
Az
+ A A
A +
0 z W N z W N
x x
Ax
x
Ax
= A A
A +
15
x x
Ax
x
Ax
A +
Dividing by the volume
N N c c
g y
and taking limit when
volume goes to zero
0
x
N
z
N
Ax Az
=
c
c
+
c
c
volume goes to zero
Introducing N
ax
and N
az
and
~ + +
c
c
= ) x ( v c ) N N ( x
c
D N
z A Bz Az A
A
AB Az

cz
c c c c
A A

c
c
~ + +
c
c
=
x
c
D ) N N ( x
x
c
D N
A
AB Bx Ax A
A
AB Ax

A
2
AB
A
z
c
D
c
v
c
=
c
16
2
AB z
x
D
z
v
c
c
Inserting the velocity profile g y p
2
A
2
AB
A
2
max
c
D
c x
1 v
c
=
c
(
(

|
.
|

\
|

2
AB max
x
D
z
1 v
c
c
(

|
.

\
o
Boundary conditions
0
c
x at
c c 0 x at ; 0 c 0 z at
A
0 A A A
=
c
o =
= = = =
For short contact times
0
x
x at
A
=
c
o =
2
A
2
AB
A
max
c
D
c
v
c
=
c
c
17
2
AB max
x
z
c
c
New boundary conditions
c c 0 x at ; 0 c 0 z at
0 A A A
= = = =
0 c x at
A
= =
Th l ti i The solution is
(
(

(
(

A
x
f
x
f 1
c
(

=
(

=
max AB max AB 0 A
A
v / D 4
erfc
v / D 4
erf 1
c
18
Local mass flux
v D
c
c
D N
max AB
0 A
A
AB A
=
c
=
z
c
x
D N
0 A
0 x
AB
0 x
Ax
t c
=
=
Total molar flow of A across the surface at x=0
v D 4
WLc dy dz N W
max AB
0 A
WL
0
Ax
= =
} }
L
WLc dy dz N W
0 A
0 0
0 x
Ax
t
} }
=
max
exp
v
L
t =
19
max
18.8 Diffusion in a three-component
system.
Diffusion through a stagnant gas
film (18.2, two gases) is extended ( , g )
to three components
W t ( i 1) i ti Water (species 1) is evaporating
into air (a mixture of nitrogen
(species 2) and oxygen (species 3)
Mass balances Mass balances
3 , 2 , 1 0
d
dN
z
= o =
o
20
, ,
dz
18.8 Diffusion in a three-component
system.
i d i Species 2 and 3 are not moving
0 N N
z 3 z 2
= =
Using Maxwell-Stefan equations.
z 3 z 2
Two concentrations are needed, since
1 x x x
3 2 1
= + +
Then
3 2 1
3
13
z 1 3
2
12
z 1 2
x
cD
N
dz
dx
x
cD
N
dz
dx
= =
21
13 12
cD dz cD dz
18.8 Diffusion in a three-component
system.
Note: D
23
is not included (no relative
motion between 2 and 3
Integrating from a arbitrary z to L
} } } }
L 3 L 2
x L x L
N dx N dx
} } } }
= =
3 2
x z
13
z 1
3
3
x z
12
z 1
2
2
dz
cD
N
x
dx
; dz
cD
N
x
dx
3 2
x z x z
22
C t ti fil Concentration profiles
Mole fraction profiles for nitrogen and oxygen
( ) ( )| | | | L N L N ( ) ( )
|
.
|

\
|
= |
.
|

\
|
=
13
z 1
L 3
3
12
z 1
L 2
2
cD
z L N
exp
x
x
;
cD
z L N
exp
x
x
M l f ti fil f t
. \ . \ 13 L 3 12 L 2
Mol fraction profile for water vapour
( ) ( )| | | | ( ) ( )
|
.
|

\
|
|
.
|

\
|
=
13
z 1
L 3
12
z 1
L 2 1
cD
z L N
exp x
cD
z L N
exp x 1 x
23
Concentration profile
N1z is determined from BC at z=0
Transcendental equation for N
1z
.
|
|

|
|
|

|
1 1
L N L N
|
.
|

\
|
|
.
|

\
|
=
13
z 1
L 3
12
z 1
L 2 10
cD
L N
exp x
cD
L N
exp x 1 x
24