Tutorial/HW Week #7

WWWR Chapters 24-25

ID Chapter 14 p
Tutorial #7
WWWR# 24.1, 24.12, 24.13,
24.15(d), 24.22.
To be discussed on March
13, 2012. 13, 2012.
By either volunteer or
class list.
Molecular Mass Transfer
Molecular diffusion
Mass transfer law components: Mass transfer law components:
Molecular concentration:
p n
A A A

M l f ti
RT
p
V
n
M
c
A A
A
A
A
= = =

Mole fraction:
(liquids,solids) , (gases)
c
c
y
c
c
x
A
A
A
A
= =
c c
For gases,
p RT p
y
A A
A
= = For gases,
Velocity:
P RT P
y
A


n
i i
n
i i
v v
Velocity:
mass average velocity,

= =
= =
i
i i
n
i
i
i i
1 1
v v
v

= i
i
1
c
n
i i
v
molar average velocity,
c
i=
=
1
V
velocity of a particular species relative to mass/molar average is
the diffusion velocity.
mol
Fl Flux:
A vector quantity denoting amount of a particular species that
passes per given time through a unit area normal to the vector,
given by Ficks First Law, for basic molecular diffusion
A AB A
c D V = J
or, in the z-direction,
A AB A
dc
D J
A
AB A
=
For a general relation in a non-isothermal, isobaric system,
dz
D J
AB z A,
dz
dy
cD J
A
AB z A
=
,
dz
Since mass is transferred by two means: Since mass is transferred by two means:
concentration differences
and convection differences from density differences and convection differences from density differences
For binary system with constant V
z
,
) (
z z A A z A
V v c J =
Thus,
) (
, , z z A A z A
V J
d
dy
cD V v c J
A
AB z z A A z A
= = ) (
Rearranging to
dz
AB z z A A z A
) (
, ,
dy
z A
A
AB z A A
V c
dz
dy
cD v c + =
,
As the total velocity, y,
) (
1
, , z B B z A A z
v c v c
c
V + =
Or
c
) (
, , z B B z A A A z A
v c v c y V c + =
Which substituted, becomes
d
) (
, , , z B B z A A A
A
AB z A A
v c v c y
dz
dy
cD v c + + =
Defining molar flux N as flux relative to a fixed z Defining molar flux, N as flux relative to a fixed z,
A A A
c v N =
And finally,
) (
A
N N y
dy
cD N + + = ) (
, , , z B z A A AB z A
N N y
dz
cD N + + =
Or generalized,
) ( y y cD N N N + + V = ) (
B A A A AB A
y y cD N N N + + V =
Related molecular mass transfer
Defined in terms of chemical potential: Defined in terms of chemical potential:
d D d
u V v
c AB c
A z z A

= =
Nernst-Einstein relation
dz RT dz
A z z A,
d
d
RT
D
c V v c J
c AB
A z z A A z A

= = ) (
, ,
dz RT
, ,
Diffusion Coefficient
Ficks law proportionality/constant
L M
J
D
z A
2
)
1
)( (

Si il ki i i i d
t
L
L L M t L
M
dz dc
D
A
z A
AB
3 2
,
)
1
1
)( ( =

= =
Similar to kinematic viscosity, v, and
thermal diffusivity, o
Gas mass diffusivityy
Based on Kinetic Gas Theory
D
1
= mean free path length u = mean speed
u D
AA

3
*
=
= mean free path length, u = mean speed
2 / 1
3
2 2 / 3
2 / 3
*
) (
3
2
AA
M
N
P
T
D
k
o t
=
Hirschfelders equation:
3
A A
M P o t
(
2 / 1
B A
M M
T
D
(

+
=
2 / 1
2 / 3
1 1
001858 . 0
D AB
AB
P
D
O
=
2
o
Lennard-Jones parameters o and c from tables, p ,
or from empirical relations
for binary systems, (non-polar,non-reacting)
2
B A
AB
o o
o
+
=
B A AB
c c c =
Extrapolation of diffusivity up to 25
2
p y p
atmospheres
2 / 3
T P
O
| | | |
2
1
1
,
1 2
,
2
1
2
2
1
T D
T D
AB AB
T
T
P
P
D D
P T P T
O
O
|
|
.
|

\
|
|
|
.
|

\
|
=
Binary gas-phase Lennard-Jones Binary gas phase Lennard Jones
collisional integral
With no reliable o or c, we can use the Fuller ,
correlation,
2 / 1
75 . 1 3
1 1
10
M M
T
|
|
.
|

\
|
+

( ) ( ) | |
2
3 / 1 3 / 1
B A
B A
AB
v v P
M M
D

+
|
.

\
=
For binary gas with polar compounds, we
( ) ( ) | |
B A

y g p p ,
calculate O by
2
196 . 0
AB
o
O O
*
196 . 0
0
T
AB
D
o
+ O = O
where
2 3
10 94 1
( )
b b
P
B A AB
T V
2 / 1
10 94 . 1
,

o o o o

= =
AB
T T c k /
*
=
2 / 1
| |
2 / 1
|
.
|

\
|
=
k
c
k
c
k
c
B A AB
. \
( )
b
T
2
3 . 1 1 18 . 1 / o k c + =
( )
) exp( ) exp( ) exp(
* * *
*
0
HT
G
FT
E
DT
C
T
A
B
D
+ + + = O
( )
) exp( ) exp( ) exp(
*
0
HT FT DT
T
and
( )
2 / 1
o o o =
3 / 1
585 . 1
|
|

|
= o
b
V
( )
B A AB
o o o =
2
3 . 1 1
|
.

\
+ o
o
For gas mixtures with several components,
1
with
n n
D y D y D y
D

+ + +
=
1
'
3 1
'
3 2 1
'
2
mixture 1
/ ... / /
1
with
y y y
y
y
+ + +
=
2
'
2
n
y y y + + + ...
3 2
22
Li id diff i it Liquid mass diffusivity
No rigorous theories
Diffusion as molecules or ions
Eyring theory
Hydrodynamic theory
Stokes-Einstein equation
T
E ti b th th i t Wilk Ch
B
AB
r
T
D
t
k
6
=
Equating both theories, we get Wilke-Chang eq.
( )
2 / 1
8
10 4 . 7
B B B AB
M D u
=

6 . 0
A
V T
=
For infinite dilution of non-electrolytes in For infinite dilution of non electrolytes in
water, W-C is simplified to Hayduk-Laudie eq.
589 . 0 14 . 1 5
10 26 13

= V D
Scheibels equation eliminates u
B
,
10 26 . 13 =
A B AB
V D
Scheibel s equation eliminates u
B
,
3 / 1
B AB
V
K
T
D
=

A
V T
(
(

|
|

|
3 / 2
3V
(
(

|
|
.
|

\
|
+ =
8
3
1 ) 10 2 . 8 (
A
B
V
V
K
A diff i it h ith t t As diffusivity changes with temperature,
extrapolation of D
AB
is by
n
| |
n
c
c
ABT
ABT
T T
T T
D
D
|
|
.
|

\
|

=
1
2
) (
) (
1
For diffusion of univalent salt in dilute solution,
we use the Nernst equation
c ABT . \ 1
) (
2
we use the Nernst equation
RT
D
2
=
F
D
AB
) / 1 / 1 (
0 0
+
+
=

Pore diffusivity
Diffusion of molecules within pores of porous
solids
Knudsen diffusion for gases in cylindrical pores
Pore diameter smaller than mean free path, and
density of gas is low
Knudsen number Kn

= Knudsen number
From Kinetic Theory of Gases,
pore
d
Kn =
y ,
AA
M
NT u
D
k 8
3 3
*
= =
A
AA
M t 3 3
But if Kn >1 then But if Kn >1, then
pore pore
KA
T
d
NT
d
u
d
D 4850
8
= = =
k
If both Knudsen and molecular diffusion exist, then
A
pore
A
KA
M
d
M
u D 4850
3 3 t
KA AB
A
A
D D
y
D
1 1 1
+

=
o
with
KA AB Ae
D D D
B
N
N
+ =1 o
For non-cylindrical pores, we estimate
A
N
2 '
Ae Ae
D D
2 '
c =
Example 6
Types of porous diffusion. Shaded areas represent nonporous solids
Hi d d diff i f l t i l t fill d Hindered diffusion for solute in solvent-filled
pores
A general model is A general model is
) ( ) (
2 1
F F D D
o
AB Ae
=
F
1
and F
2
are correction factors, function of pore
diameter,
s
d
F is the stearic partition coefficient
pore
s
d
=
F
1
is the stearic partition coefficient
2
2
1
2
( )
( ) (1 )
pore s
d d
F
d
t

t

= =
pore
d t
F
2
is the hydrodynamic hindrance factor, one
equation is by Renkin,
5 3
2
95 . 0 09 . 2 104 . 2 1 ) ( + = F
Example 7
Convective Mass Transfer
Mass transfer between moving fluid with
surface or another fluid
Forced convection
Free/natural convection Free/natural convection
Rate equation analogy to Newtons cooling
i equation
A c A
c k N A =
Example 8
Differential Equations
Conservation of mass in a control volume:
c
( )
}}} }}
=
c
c
+
. . . .
0
v c s c
dV
t
dA n v
Or,
in out + accumulation reaction = 0
For in out For in out,
in x-dir,
x x A x x x A
z y n z y n A A A A
A + , ,
in y-dir,
y y A y y y A
z x n z x n A A A A
A + , ,
in z-dir,
z z A z z z A
y x n y x n A A A A
A + , ,
For accumulation,
z y x
t
A
A A A
c
c
t c
For reaction at rate r
A
For reaction at rate r
A
,
z y x r
A
A A A
Summing the terms and divide by AxAyAz,
, , , , , ,
0
A x x x A x x A y y y A y y A z z z A z z
A
A
n n n n n n
r
x y z t

+A +A +A

c
+ + + =
A A A c
with control volume approaching 0,
c c c c
, , ,
0
A
A x A y A z A
n n n r
x y z t
c c c c
+ + + =
c c c c
We have the continuity equation for We have the continuity equation for
component A, written as general form:
c
0 =
c
c
+ V
A
A
A
r
t

n
For binary system,
( )
( )
( )
n n 0
A B
r r
c +
V + + + =
but
( ) ( )
n n 0
A B A B
r r
t
V + + + =
c
v v v n n = + = +
but
and
v v v n n = + = +
B B A A B A
B A
r r =
So by conservation of mass So by conservation of mass,
0 =
c
c
+ V

v
Written as substantial derivative,
ct

0 = V + v

Dt
D
For species A,
Dt
D
0 = V +
A A
A
r
Dt
D
j
e
In molar terms In molar terms,
0 =
c
c
+ V
A
A
A
R
t
c
N
For the mixture,
ct
( )
( )
( )
0 ) ( = +
c
+ c
+ + V
B A
B A
B A
R R
t
c c
N N
And for stoichiometric reaction,
c
0 ) ( = +
c
c
+ V
B A
R R
t
c
cV