10.

October 2012
Chapter 3
Diffusion in Concentrated Solutions
Dr. K. Wegner - Lecture 10.10.2012
Mass Transfer
Mass Transfer Diffusion in Concentrated Solutions 2
3. DIFFUSION IN CONCENTRATED SOLUTIONS
Diffusion causes convection in fluids
Convective flow occurs because of pressure gradients (most
common) or temperature differences (buoyancy or free or natural
convection). However even in isothermal and isobaric systems,
convection can occur due to diffusion.
Maxwell (1860) said: Mass transfer is due partly to the motion of
translation and partly that of agitation.
Diffusion and convection always occur together in fluids.
3.1 Theory
Mass Transfer Diffusion in Concentrated Solutions
Example: Evaporation of Benzene:
3
At 6C the benzene vapor is dilute and
evaporation is limited by diffusion.
At 80.1C benzene boils (p = 1atm).
Evaporation is controlled by convection.
At 60C an intermediate case occurs in which
both diffusion and convection are important.
Mass Transfer Diffusion in Concentrated Solutions
Analysis of the case at 60C:
4
Concentration of benzene (species 1) and air
(species 2) at z = h:
c
1,h
= c
1,
( 0); c
2,h
max
p
1,h
= p
1,
( 0); p
2,h
p
(air blows away and dilutes benzene vapor).
At z = 0:
c
1,0
= f (T,p) > c
1,h
and c
2,0
< c
2,h
p
1,0
= f (T,p) > p
1,h
and p
2,0
< p
2,h
Mass Transfer Diffusion in Concentrated Solutions 5
The difference in concentrations (or
partial pressures) between 0 and h gives
rise to upward diffusion of benzene from
the liquid surface and downward
diffusion of air.
Since the benzene surface is considered
impermeable to air, a convective upward-
pointing flux must compensate the
downward diffusive flux of air!
This is the Stefan flow !
NOTE: This convection also transports benzene molecules!
Mass Transfer Diffusion in Concentrated Solutions
Determine concentration profile and flux for the 60C case
6
Mass balance for species i at steady state:
) z z ( J ) z z ( J ) z ( J ) z ( J
diff , i conv , i diff , i conv , i
A + + A + = +
Diffusive flux:
dz
dc
A D J
diff i
=
,
Convective flux with velocity u:
u A c J
i conv i
=
,
Mass Transfer Diffusion in Concentrated Solutions 3-7
For z 0 we obtain:
0
2
2
=
|
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c

z
c
D
z
c
u
i i
For practicability we transform molar concentrations into mole
fractions:
( ) c
c
V c c
V c
n n
n
y
1
2 1
1
2 1
1
1
=
+

=
+
=
(1)
If c is given as a mass concentration the transformation into
mole fractions is:
1
1
1
M
M c
y


= with the average molar mass
i
k
i
M y M

=
1
Mass Transfer Diffusion in Concentrated Solutions 3-8
So (1) can be rewritten as: 0
2
2
=
(

|
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c

z
y
D
z
y
u c
i i
(2)
Integration of eq. (2) for species 1 (benzene):
C
z
y
D y u c =
(

|
.
|

\
|
c
c

1
1
(3)
The two terms are the convective and diffusive molar flux densities.
The sum of the molar fluxes is constant.
Integration of eq. (2) for species 2 (air) with
1 2
1 y y =
( ) C
z
y
D y 1 u c
1
1
'
=
(

|
.
|

\
|
c
c
+
(4)
Mass Transfer Diffusion in Concentrated Solutions 3-9
Since air does not accumulate and cannot penetrate the benzene
surface, the total (overall) molar flux of air is zero. Thus 0 =
'
C
Eq. (4) is rewritten as: ( )
|
.
|

\
|
c
c
=
z
y
u
D
y
1
1
1 (5)
Integration of (5) with B.C. y
1
= y
1,0
at z = 0:
( ) ( )
z
D
u
e y y =
0 , 1 1
1 1
(6)
Determine velocity u with B.C. y
1
= y
1,h
at z = h:
|
|
.
|

\
|

=
0 , 1
, 1
1
1
ln
y
y
h
D
u
h
(7)
Mass Transfer Diffusion in Concentrated Solutions 3-10
Inserting eq. (7) into (5) gives the concentration profile:
( )
( )
h
z
h
y
y
y
y
|
|
.
|

\
|

0 , 1
, 1
0 , 1
1
1
1
1
1
(8)
With the concentration profile and eq. (3) we can obtain the total
molar flux:
|
|
.
|

\
|

= =
0 , 1
, 1
1
1
ln
y
y
h
D c
C j
h
tot
(9)
This type of approach leads to the Stefan-Maxwell equations for
multi-component diffusion in concentrated solutions.
Mass Transfer Diffusion in Concentrated Solutions
Separating Convection from Diffusion Cusslers Approach
3-11
Now, Cussler treats this topic slightly different (but gets to the
same results).
Assume that these two effects are additive:
|
|
.
|

\
|
+
|
|
.
|

\
|
=
|
|
.
|

\
|
convection by
d transporte mass
diffusion by
d transporte mass
d transporte
mass total
If the total mass flux is n
1
, the mass transported per area per time
relative to fixed coordinates:
1 1 1
v c n =
where v
1
is the average solute velocity (velocity due to convection
and superimposed diffusion).
Mass Transfer Diffusion in Concentrated Solutions 3-12
The total average solute velocity can be split into a part due to
diffusion and one due to convection, called reference velocity v
a
:
( )

convection
a
1
flux
diffusive
a
1
a
1
a
1 1 1
v c j v c v v c n + = + =
The art is to select v
a
in such a way that v
a
=0.
For example v
a
is the velocity of the solvent because the solvent is
usually in excess so its transfer is minimal (in other words the
difference in solvent concentration is too small across the solution).
That way we eliminate convection and deal with a SIMPLER
problem.
Mass Transfer Diffusion in Concentrated Solutions 3-13
Two-bulb apparatus (Diaphragm-
cell) for understanding different
definitions of reference velocities.
Volume average velocity = 0
Molar average velocity = 0
Mass average velocity 0
Volume average velocity = 0
Molar average velocity 0
Mass average velocity 0
Mass Transfer Diffusion in Concentrated Solutions 3-14
For gases (e.g. H
2
and N
2
) at equal T and p the number of
moles is always the same in both sides. Similarly the volume in
both sides is the same. As a result, the
v
0
= 0 volume average velocity
v
*
= 0 molar average velocity
v = 0 mass average velocity,
because the masses of N
2
and H
2
are different. As a result,
as time goes by the center of mass in the two-bulb
apparatus moves away from the bulb containing N
2
initially.
Thus the mass average velocity v is not zero.
Mass Transfer Diffusion in Concentrated Solutions 3-15
For liquids: The volume is nearly always constant.
v
0
= 0 volume average velocity
v = 0 mass average velocity. This is usually correct as liquid
densities differ little.
e.g.
H2O
=1 g/cm
3

Glycerol
=1.1 g/cm
3
However, the molar concentration is usually quite different following
large differences in molecular weight.
e.g. MW
H2O
=18 g/mol and
MW
Glycerol
=92 g/mol
So v
*
=0 molar average velocity for liquids.
In conclusion: For gases use as reference velocity v
a
the v
0
or v
*
,
while for liquids use v
0
or v.
Mass Transfer Diffusion in Concentrated Solutions 3-16
Mass Transfer Diffusion in Concentrated Solutions 3-17
Table legend:

i
: mass fraction of species i
y
i
: mole fraction of species i
i
i
V c
: volume fraction of species i,
i
V where is the partial specific volume of species.
Precisely: Partial specific volume:
j
m T p
i
i
m
V
V
, ,
|
|
.
|

\
|
c
c
=
Partial molar volume:
j
n T p
i
i
n
V
V
, ,
|
|
.
|

\
|
c
c
=
The partial specific or molar volume expresses how much a volume
changes upon addition of a certain mass or number of moles of a
given component.
Mass Transfer Diffusion in Concentrated Solutions 3-18
Partial molar volume for ideal gases (pV = nRT) :
( )
c p
T R
n
p
RT
n n
n
V
V
n T p
n T p
1
2
2
, ,
1
2 1
, ,
1
1
=

=
|
|
|
|
.
|

\
|
c
(

+ c
=
|
|
.
|

\
|
c
c
=
Mass Transfer Diffusion in Concentrated Solutions
3.2 Examples for Parallel Diffusion and Convection
3-19
Example 3.2.1: Fast Diffusion through a stagnant film
Goal: Calculate the flux and
the concentration profile
Now both diffusion and
convection are important!
Remember that at intermediate
temperatures both diffusion
and convection affect the
evaporation of benzene (or any
other solute).
Mass Transfer Diffusion in Concentrated Solutions 3-20
1. Step: Mass balance
|
|
.
|

\
|
A +

|
|
.
|

\
|
=
|
|
.
|

\
|
A z z at out
d transporte solute
z at in
d transporte solute
z A volume in
d accumulate solute
( )
z z 1 z 1 1
| An | An c z A
t
A +
= A
c
c
Divide by AAz and as volume 0
z
n
c
t
1
1
c
c
=
c
c
At steady state:
z
n
0
1
c
c
=
Mass Transfer Diffusion in Concentrated Solutions 3-21
Now the flux is affected by both diffusion and convection. For
simplicity we choose v
a
=v
0
(volume average velocity)
) v V c v V c ( c
dz
dc
D v c j n
2
2
2 1
1
1 1
1 0
1 1 1
+ + = + =
2. Step: Choose and simplify mass transport equation
Note that n
1
=c
1
v
1
and n
2
=c
2
v
2
The total average flux of the solvent (air) is zero, since it cannot
penetrate into the liquid phase and does not accumulate.
Therefore n
2
=0 and v
2
=0.
(Cussler mentions that the solvent vapor is stagnant and therefore
n
2
=0 and v
2
=0. This does not make sense physically, though.)
Mass Transfer Diffusion in Concentrated Solutions 3-22
So
1
1
1
1
1
n V c
dz
dc
D n + =
If the vapor is an ideal gas, then
( )
1
1
1
2 1
1
1
V c
c
c
V c c
V c
y = =
+

=
dz
dc
D ) V c 1 ( n
1
1
1 1
=
dz
dy
Dc ) y 1 ( n
1
1 1
=
(1)
3. Step: Boundary conditions
z=0: y
1
=y
10
z=L: y
1
=y
1L
(2)
(3)
or
and
Mass Transfer Diffusion in Concentrated Solutions 3-23
Solve eqn. (1) subject to BCs to determine n
1
|
|
.
|

\
|

=
10
1
1
y 1
y 1
ln
Dc
n

(4)
Note that doubling the concentration difference DOES NOT double
the flux, as in dilute systems.
Integrating eq. (1) also for z=0 to z and y
1
=y
10
to y
1
and assuming
that n
1
does not change with height z (which is a fair assumption
here as the cross-sectional area does not change) gives:

z
10
1
10
1
y 1
y 1
y 1
y 1
|
|
.
|

\
|

(5)
Concentration profile
Mass Transfer Diffusion in Concentrated Solutions 3-24
|
|
.
|

\
|

|
|
.
|

\
|

= =
10
1
z
10
1 10
y 1
y 1
ln
y 1
y 1 y 1
Dc
dz
1
dy
Dc
1
j

(6)
|
|
.
|

\
|

= =
0 , 1
, 1
1
1
ln
y
y
h
D c
C j
h
tot
Compare to our initial result for combined diffusion and
convection of benzene (page 3-10):
Eq. 6 gives the same results assuming y
1L
=y
1h
0 and z=L=h
The direct approach and the one using the reference velocity give
the same results!
Mass Transfer Diffusion in Concentrated Solutions 3-25
Now does this result reduce to that for dilute solutions?
Expansion into series for small y (dilute system small conc. y):
( )
( ) ( )( )
+
+ + +
+ =

3 2
a
y
! 3
2 a 1 a a
y
! 2
1 a a
y a 1 y 1
(7)
(8)
(9)
( )
( ) ( )( )
y a 1 y
! 3
2 a 1 a a
y
! 2
1 a a
y a 1 y 1
3 2
a
~ +

+ =
Here a=1:
y 1
y 1
1
+ ~

( ) y
3
y
2
y
y y 1 ln
3 2
~
(

+ + + =
0 0
Mass Transfer Diffusion in Concentrated Solutions 3-26
Lets apply eqn. (8) to eqn. (5)
( )( ) | | | |

z
10 1
z
10 1
10
1
y y 1 y 1 y 1
y 1
y 1
+ = + + =

( )

z
10 1 10 1
y y 1 ) y 1 ( y 1 + =
( ) ( )

1 10 10 10 1 10
y y
z
y 1 y
z
y
z
1 y 1 +
(

~ + ~
If we multiply both sides of eqn. (10) with c
(10)
) c c (
z
c c
10 1 10 1
+ =

(11)
with approx. (7) becomes
Mass Transfer Diffusion in Concentrated Solutions 3-27
Likewise for the flux from eqn. (4)
| |

| | ) c c (
D
y y
Dc
) y 1 ln( ) y 1 ln(
Dc
n
1 10 10 1
9 Eq
10 1 1

= + =
=
Eqn. (11) and (12) are identical to the dilute limit ones!
(12)
Mass Transfer Diffusion in Concentrated Solutions
Example 3.2.2: Calculate the error associated with the neglect of
diffusion-driven convection when estimating the evaporation rate of
benzene @ 6C and @ 60C.
a) At 6C the saturation vapor pressure is p
1
(sat) = 37 mmHg
Mole fraction
049 . 0
760
37
p
) sat ( p
c
c
y
1 1
10
= = = =
Total flux at steady-state for concentrated solution:

c D
05 . 0
049 . 0 1
0 1
ln
c D
y 1
y 1
ln
c D
n
10
1
1
=
|
.
|

\
|

=
|
|
.
|

\
|

=
Total flux for dilute solution:
( ) ( )


c D
049 . 0 0 049 . 0
c D
y y
c D
j n
1 10 1 1
= = = = Only 2% error!
Mass Transfer Diffusion in Concentrated Solutions 3-29
b) At 60C the saturation vapor pressure is p
1
(sat) = 395 mmHg
760
395
y
10
=
Mole fraction
Concentrated solution:

c D
73 . 0
760 / 395 1
0 1
ln
c D
y 1
y 1
ln
c D
n
10
1
1
=
|
.
|

\
|

=
|
|
.
|

\
|

=
Dilute solution:
( )


c D
52 . 0 0
760
395 c D
y y
c D
j n
1 10 1 1
=
|
.
|

\
|
= = =
There is 40% error !!
Mass Transfer Diffusion in Concentrated Solutions 3-30
Example 3.2.3: Catalytic cracking of methane
Methane gas is cracked at the surface of a solid catalyst forming
hydrogen and a solid carbon deposit.
Goal: Total methane (molar) flux per unit area at steady state?
n
1 Catalyst
surface
n
2
z
0

CH
4
2H
2
Carbon
deposit
CH
4(g)
C
(s)
+ 2 H
2(g)
Mass Transfer Diffusion in Concentrated Solutions 3-31
Choose and simplify mass transport equation:
Note: For processes with chemical reactions, it is best to use the
molar flux and the molar average velocity!
Thus, from Table 3.2.1:
*
1
1
*
1 1 1
v c
dz
dc
D V c j n + = + =
(1)
with
c
n n
v y v y v
2 1
2 2 1 1
*
+
= + =
(2)
Now 1 mole of CH
4
gives 2 moles of H
2
, flowing in the opposite
direction. Therefore,
1 2
2 n n = in eq. (2):
c
n
v
1
*
=
and
c
n
c
dz
dc
D n
1
1
1
1
=
Mass Transfer Diffusion in Concentrated Solutions 3-32
Use molar fractions
c
c
y
1
1
=
1 1
1
1
n y
dz
dy
c D n =
( )
dz
dy
c D y n
1
1 1
1 = +
(3)
B.C.: z = 0: y
1
= 0 (due to decomposition)
z = L: y
1
= y
1,L
(some measured conc. at L)
Integration of (3) subject to B.C.s yields:
( )
L
y
L
Dc
n
1 1
1 ln + =
Or the general form if y
1,0
0:
|
|
.
|

\
|
+
+
=
0 , 1
, 1
1
1
1
ln
y
y
L
Dc
n
L
Mass Transfer Diffusion in Concentrated Solutions 3-33
Example 3.2.4: Fast Diffusion into Semi-Infinite Slab
A volatile liquid solute evaporates into a long capillary
Initially the capillary contains no
solute. As the solute evaporates
the interface between the vapor
and the liquid solute drops.
Goal: Calculate the solute
evaporation rate accounting for
diffusion induced convection and
the effect of moving interface.
Mass Transfer Diffusion in Concentrated Solutions 3-34
Mass balance:
|
.
|

\
|
|
.
|

\
|
= |
.
|

\
|
A out transport
solute
in transport
solute
z A in
ion accummulat solute
( ) ( ) ( )
z z
1
z
1 1
n A n A z A c
t
A +
= A
c
c
Divide by A Az and as Az 0
z
n
t
c
1 1
c
c
=
c
c
(1)
There is no solvent (air) flow across the capillary, blowing the solute
away. As a result, the solute accumulates in the capillary.
Mass Transfer Diffusion in Concentrated Solutions 3-35
Choose and simplify mass transport equation:
n
1
= j
1
+c
1
v
0
2
2
1
1 2
2
2 1
1
1
0
V n V n v V c v V c v + = + = with
The solvent gas does not dissolve in the liquid, thus at the
interface (z=0): n
2
= 0.
0
1
2
1
2
1
v c
z
z
c
D
t
c
c
c

c
c
=
c
c
In (1):
( )
0 z
1
0 z
1
1
1
z
c
D n V c 1
=
=
c
c
=
(2)
(3)
z
c
V c 1
z
c
V D
z
c
D
t
c
1
0 z
1
1
1
1
2
1
2
1
c
c
|
|
|
|
|
.
|

\
|

|
|
.
|

\
|
c
c
+
c
c
=
c
c
=
(4)
Mass Transfer Diffusion in Concentrated Solutions 3-36
t = 0 z > 0 c
1
= 0
t > 0 z = 0 c
1
= c
1
(sat)
z = c
1
= 0
Boundary conditions:
Define combined variable
t D
z

= ,
4
( ) 0
d
dc
2
d
c d
1
2
1
2
=
,
u , +
,
(5)
with B.C. , = 0 c
1
= c
1
(sat)
, = c
1
= 0
Mass Transfer Diffusion in Concentrated Solutions 3-37
where
0
1
1
1
1
V c 1
c
V
2
1
= ,
|
|
|
|
|
.
|

\
|

|
|
.
|

\
|
, c
c
= u
(6)
In eq. (5) u is a dimensionless velocity characterizing the
convection by diffusion and the movement of the interface. Note
that if u = 0 the problem reduces to that of diffusion in dilute
concentrations !!
Eqn. (5) is integrated to give:
( ) | |
2
1
) ( exp t tan cons
c
u , =
, c
c
Mass Transfer Diffusion in Concentrated Solutions
2
nd
integration and insertion of B.C.:
( )
( ) u +
u ,
=
erf
erf
sat c
c
1
1
) (
1
1
(7)
eqn. (6) (7):
( ) ( ) | |
1
2
1
1
exp erf 1
1
1 ) sat ( c V

|
|
.
|

\
|
u u u + t
+ =
Calculate now the interfacial flux
0 z
1
1
1
4 . eqn
0 z 1 1
V c 1
z
c
D n N
=
=
|
|
|
|
|
.
|

\
|

|
|
.
|

\
|
c
c
=
=
| |
( ) u +
u

t =
erf 1
exp
) sat ( c V 1
1
) sat ( c t / D
2
1
1
it lim dilute
1

Mass Transfer Diffusion in Concentrated Solutions 3-39