6/4/2013

1
Mass Transfer Principles
1. Introduction
2. Mass Transfer Principles
3. Equilibrium Stage Operations
4. Distillation
5. Absorption
6. Extraction
7. Leaching
The objective is:

Recognize and be able to use equilibria and material
and energy balances to carry out process calculations
Recognize the mass transfer concept in separation
process and their estimation
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Mass Transfer Basics
Basic mass transfer equation:

Mass transfer rate = (Area) (Mass transfer coefficient) (Driving force) (1)

Eq. 1 can be written in equation form as follows

Rate = K
y
a (y
i
* y
i
) (2)

or Rate = K
x
a (x
i
* x
i
) (3)

where
K
y
= mass transfer coefficient in gas phase
K
x
= mass transfer coefficient in liquid phase
a = contacting area
x
i
or y
i
= concentration of species i at any time
x
i
* y
i
* = concentration of species i at equilibrium

When a system contains two or more components
whose concentrations vary from point to point,
there is a natural tendency for mass to be
transferred, minimizing the concentration
differences within a system.

Mass transfer - When a component in a mixture
migrates in the same phase or from phase to
phase because of a difference in concentration

Introduction
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Introduction
The transport of one constituent from a region
of higher concentration to that of a lower
concentration is called mass transfer.

Rate of a transfer process = driving force
resistance
Possible driving force for mass transfer
Concentration different
Pressure different
Electrical gradient

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Examples of mass transfer
Evaporation of water in the open pail to
atmosphere
Coffee dissolves in water
O
2
dissolves in the solution to the
microorganism in the fermentation process
Reaction occurs when reactants diffuse
from the surrounding medium to the
catalyst surface
The mechanism of mass transfer involves
both molecular diffusion and convection.

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Mass transfer
Molecular diffusion
Convective mass
transfer

Gases
Liquid
Solid

Types of Mass Transfer
Molecular diffusion
Transfer of individual molecules through a fluid
by random movement
From high conc. to low conc.
e.g. a drop of blue liquid dye is added to a cup of
water- the dye molecules will diffuse slowly by
molecular diffusion to all parts of the water.
- to increase this rate of mixing of the dye, the
liquid can be mechanically agitated by a spoon
and convective mass transfer will occur

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Convective mass transfer
Using mechanical force or action to
increase rate of molecular diffusion
e.g- stirred the water to dissolve coffee
during coffee making

Molecular Diffusion
Transfer of individual molecules
through a fluid by random, individual
movements of the molecules
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Molecular Diffusion
The basic of diffusion(Ficks Law) was
enunciated by Adolf Eugen Fick, a
physiologist in 1885

the molar flux of a species relative to an
observer moving with molar average
velocity is proportional to the conc.
gradient of the species
Molecular Diffusion
Diffusion of molecules when the bulk fluid is
stationary given by Ficks Law :
dz
dx
cD J
A
AB
A =
*
Molar flux of component A (kgmol A/s.m
2
)

Molecular diffusivity of the molecule A in B (m
2
/s)

Total conc. of A and B (kgmol A+B/m
3
)

Mole fraction of A
A J
*
AB
D
c
A
x
(1)
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Molecular Diffusion
Ficks Law for molecular diffusion of mass at constant
total concentration c
A
= x
A
c:
dz
dc
D J
A
AB
Az
*
=
Molar flux of component A in the z direction due to
molecular diffusion (kgmol A/s.m
2
)
Molecular diffusivity of the molecule A in B (m
2
/s)
Concentration of A (kgmol/m
3
)
Distance of diffusion (m)
Az
*
J
AB
D
A
c
z
(2)
If c is varies, an average value is often used with equation (2).
Other driving forces (besides conc.) for diffusion also occur because of T,
P, electrical potential and other gradients. (transport phenomena TB)
Example
Molecular Diffusion of Helium in Nitrogen. A
mixture of He and N
2
gas is contained in a
pipe at 298 K and 1 atm total pressure which
is constant throughout. At one end of the
pipe at point 1 the partial pressure p
A1
of He
is 0.60 atm and at the other end 0.2 m (20
cm) p
A2
= 0.20 atm. Calculate the flux of He
at steady state if D
AB
of the He-N
2
mixture is
0.687 x 10
-4
m
2
/s (0.687 cm
2
/s).

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Integrate the equation:



From ideal gas law, p
A
V = n
A
RT,
1 2
2 1
) (
z z
c c D
J
A A AB
A

=
) (
) (
1 2
2 1
z z RT
p p D
J
A A AB
A

=
V
n
RT
p
c
A A
A
= =
1
1
) 0 20 . 0 )( 298 ( 8314
) 10 027 . 2 10 08 . 6 )( 10 887 . 0 (
4 4 4

=

x x x
J
A
= 5.63 x 10
-6
kgmolA/s.m
2
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Think of the last time that you washed the dishes.
You placed your first greasy plate into the water,
and the dishwater got a thin film of oil on the top of
it, didnt it? Find the flux, J, of oil droplets through
the water to the top surface. The sink is 18 cm
deep, and the concentration of oil on the plate is 0.1
mol/cm
3
. Assume that there is no oil at the top of
the sink yet.
Exercise
Answer:
To solve this problem, we will need to apply the mass transfer equation we
just learned.



where: D
AB
= 7 x 10
-7
cm
2
/s
dc
A
= concentration at the top of the sink the concentration of oil on the plate.

The concentration at the top of the sink = 0

The concentration of oil on the plate = 0.1 mol/cm
3

dc
A
= 0 0.1 = -0.1 mol/cm3

dz = the depth of the sink = 18 cm

Since we know all of the numbers needed, we can calculate the flux.
J = -(7 x 10
-7
cm
2
/s) * (-0.1 mol/cm3) / (18 cm)
J = 4 x 10
-4
mol / (cm
2
s)
dz
dc
D J
A
AB
Az
*
=
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Convective Mass Transfer
When fluid flowing outside a solid surface
in forced convection motion, rate of
convective mass transfer is given by:
) c c ( k N
Li L c A
=
1
Mass-transfer coefficient (m/s)
Bulk fluid concentration (kgmol A/m
3
)
Concentration in the fluid next to the surface of the
solid
c
k
1 L
c
Li
c
(2)
k
c
depends on >>>>>system geometry, fluid properties and flow velocity
The objective is:

Recognize and be able to use equilibria and material
and energy balances to carry out process calculations
Recognize the mass transfer concept in separation
process and their estimation
Learning Outcomes
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Diffusion in Gases p 414
Outlines:
1. Equimolar counter diffusion in gases
2. General case for diffusion of gases A and B
plus convection
3. Special case for A diffusing through
stagnant, non-diffusing B
4. Diffusion through varying cross-sectional
area
5. Diffusion coefficients for gases
1. Equimolar counter-diffusion
Consider:
2 gases A and B
At constant total
pressure P
Molecular diffusion at
steady-state
Partial pressures:
2 1
A A
p p >
1 2
B B
p p >
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Net moles A and B diffusing right to left (and vice versa) are equal
since total pressure P is constant,
Bz
*
Az
*
J J =
Ficks law for B for constant total concentration c,
Since total pressure P is constant (P=P
A
+ P
B
), then
B A
c c c + =
B A
dc dc =
dz
dc
D J
B
BA
B
*
=
(3)
(4)
(5)
1. Equimolar counter-diffusion
Combining (1), (3) and (4)
( )
dz
dc
D
dz
dc
D
B
BA
A
AB
=
(6)
Substituting (5) into (6) and canceling
BA AB
D D = (7)
for binary gas mixture of A and B, the diffusivity coefficient D
AB
for
A diffusing into B is the same as D
BA
for B diffusing into A
1. Equimolar counter-diffusion
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Exercise
Check example 6.2-1
Equimolar counter diffusion is occurring at steady
state in a tube 0.11 m long containing N2 and CO
gases at the total pressure of 1.0 atm abs. The
partial pressure of N2 is 80mm Hg at one end and
10 mmHg at the other end. Given the D
AB
at 298K
is 2.05 x 10
-5
m
2
/s

a) Calculate the flux in kg mol/s.m
2
at 298 K for N2
b) Repeat at 473 K. Given that D
AB
at 493K is 4.60
x 10
-5
m
2
/s.
Exercise
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2. General diffusion & convection
Consider a bulk fluid of binary mixture A and B moving in the z-direction
with an average bulk fluid velocity v
m
m/s, as shown in the Figure below.
Concentration of A at any point in the mixture is C
A
kg-mole/m
3
.
Movement of A is now due to 2 contributions:
Molecular diffusion J
A
= - D
AB
.(dc
A
/dz) (kg-mole/m
2
.s)
Bulk movement of fluid C
A
v
m
(kg-mole/m
3
. m/s)

v
m
2. General diffusion & convection
For diffusion in stationary fluid, the diffusion flux J
*
A
passing a fixed
point from left (high conc.) to right (low conc.) can be expressed in
terms of velocity of diffusion of A,
A Ad
A
*
c v J =
(m/s)(kgmol A/m
3
) (kgmol A/sm
2
)
Diffusion velocity
of A
If convective flow (to the right) presents, A is diffusing at velocity
v
Ad
plus the convective velocity of the bulk fluid. Hence,
M Ad A
v v v + =
Convective
velocity of the
bulk fluid
Velocity of A
relative to a
stationary point
(8)
(9)
v
m
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2. General diffusion & convection
Multiplying by c
A
,
M A Ad A A A
v c v c v c + =
Hence,
M A
A
*
A
v c J N + =
If N = total convective flux of the whole stream relative to the
stationary point, then
B A M
N N cv N + = =
c
N N
v
B A
M
+
=
(11)
(12)
(10)
2. General diffusion & convection
Substituting equation (11) and Ficks law into (12),
( )
B A
A A
AB A
N N
c
c
dz
dx
cD N + + =
Note:
For Equimolar counter-diffusion,
Hence,
B A
N N =
dz
dx
cD N
A
AB A
=
Convection
term
Diffusion
term
(13)
This is the general equation describing mass transfer of component-A by
diffusion through moving bulk fluid. It allows one to calculate the mass
transfer rate (molar flux, e.g. in kg-mole/m
2
.s) between 2 points.
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3. Stagnant, non-diffusing B
3. Stagnant, non-diffusing B
For A diffusing in stagnant, non-diffusing B, in equation (12) set
0 =
B
N
( ) 0 + + =
A
A A
AB A
N
c
c
dz
dx
cD N
If total pressure is kept constant P
(14)
RT
P
c = P x p
A A
=
P
p
c
c
A A
=
Substituting into (14)
A
A A AB
A
N
P
p
dz
dp
RT
D
N + =
(15)
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3. Stagnant, non-diffusing B
Re-arranging and integrating
1
2
1 2 A
A AB
A
p P
p P
ln
) z z ( RT
P D
N

=
(16)
Or another form P =p
A1
+ p
B1
=p
A2
+ p
B2
,
p
B1
=P-p
A1
and p
B2
= P-p
A2
( )
2 1
1 2
A A
BM
AB
A
p p
p ) z z ( RT
P D
N

= (17)
dz
dp
RT
D
P
p
N
A AB A
A
=
|
|
.
|

\
|
1
p
p
dp
RT
D
dz N
A
A
p
AB
z
z
A
p
=
} }
1
2
1
2
1
| | ) /( ) ( ln ) / ln(
1 2
2 1
1 2
1 2
A A
A A
BM B B
B B
BM
p P p P
p p
p p p
p p
p


=

=
Water
vapor
example
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M Azmi Bustam
Sphere to surrounding medium
Evaporation of a drop of liquid
Evaporation of a ball of naphthalene
Diffusion of nutrients to a sphere-like micro-
organism in a liquid
Conduit of non-uniform csa
4. Varying cross-sectional area
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4. Varying cross-sectional area
4. Varying cross-sectional area
Define
A
N
N
A
A
=
Where

Kg moles of A diffusing per second (kgmol/s)

Cross-sectional area through which the diffusion
occurs
A N
A
At steady-state, will be constant but not for varying
area.
A N
A
(18)
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4. Varying cross-sectional area
1. Diffusion from a sphere
BM
A A AB
A
A
p
P p
RTr
P D
N
r
N
2 1
1
1 2
1
4

= =
t
If is small compared to (a dilute phase),
Also, setting , diameter, and
(19)
1 A
p
P
P p
BM
~
1 1
2 D r =
RT / p c
A A 1 1
=
( )
2 1
1
1
2
A A
AB
A
c c
D
D
N =
(20)
2
4 r A t =
4. Varying cross-sectional area
2. Diffusion through a conduit of non-uniform csa
( )dz P / p
dp
RT
D
r
N
N
A
A AB A
A

= =
1
2
t
Defining
1
1 2
1 2
r z
z z
r r
r +
|
|
.
|

\
|

=
} }

=
(

+
|
|
.
|

\
|

2
1
2
1
1
2
1
1 2
1 2
z
z
p
p A
A AB
A
A
A
P / p
dp
RT
D
r z
z z
r r
dz N
t (21)
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5. Diffusion coefficients for gases
a) Experimental determination
( )
) ( 2
2 1
2 2
A A AB A
BM o F
F
p p P D M
RTp z z
t

=

5. Diffusion coefficients for gases
a) Experimental determination
( )
( )( )
(

+
=

t
V V A / L
V V D
exp
c c
c c
AB
av
av
1 2
2 1
0
2
2
Where is the average concentration value at equilibrium av
c
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5. Diffusion coefficients for gases
b) Experimental diffusivity data
Available in Perry and Green or Reid at al.
Typical data as in Geankoplis pg 424.
D
AB
, range from 0.05 x 10
-4
m
2
/s, to about 1.0 x 10
-4
m
2
/s(H
2
)
5. Diffusion coefficients for gases
c) Prediction of diffusivity for gases
Semi-empirical method of Fuller et al.
( )
( ) ( ) | |
2
3 1 3 1
2 1 75 1 7
1 1 10
/
B
/
A
/
B A
.
AB
v v P
M / M / T
D

+
+
=

Where
Sum of structural volume increments
A
v
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5. Diffusion coefficients for gases
d) Schmidt number of gases
AB
Sc
pD
N

=
The Schmidt number of a gas mixture of dilute A in B is defined by:
Where
Viscosity of the gas mixture (B for dilute) (Pas or
kg/ms)
Diffusivity (m
2
/s)
Density of the mixture (kg/m
3
)

AB
D
p
It is dimensionless. For gases, values range from 0.5 2.0.
Diffusion in Liquids p427
Outlines:
1. Introduction
2. Equations for diffusion in liquids
3. Diffusion coefficients for liquids
4. Prediction of diffusivities in liquids
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1.Introduction
Very important in many industrial process e.g.
liquid-liquid extraction, solvent extraction, gas
adsorption and distillation
Molecular diffusion in liquid slower than gases;
- molecules in a liquid are very close compared
to a gas
-diffusion in a gas 10
5
times greater than in a
liquid


Diffusion in Liquids
2.Equations for diffusion in Liquid
Kinetic theory of liquid is partially
developed, equations for diffusion in
liquids similar to gases
The diffusivities are often dependent on
conc. of the diffusing components


Diffusion in Liquids
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a. Equimolar counter diffusion

1 2
2 1
1 2
2 1
) ( ) (
z z
x x c D
z z
c c D
N
A A av AB A A AB
A

=
Diffusion in Liquids
Where,
2 /
2 1
2 1
|
|
.
|

\
|

=
|
.
|

\
|
=
M M M
c
av
av

c
A1
conc. A at
point 1
x
A2
mole frac.
A at point 1

c
av
average total
conc. A + B in
kgmol/m
3


b. Diffusion of A through nondiffusing B,

in gas

Rewrite in terms of conc. by substituting
Where p
BM
is log mean partial conc. of B between the location z
2
and z
1

BM
A A av AB
A
x z z
x x c D
N
) (
) (
1 2
2 1

=
Diffusion in Liquids
Where,
) / ln(
1 2
1 2
B B
B B
BM
x x
x x
x

=
( )
2 1
1 2
A A
BM
AB
A
p p
p ) z z ( RT
P D
N

=
P
p
x
RT
p
c
RT
P
c
BM
BM
A
A AV
= = = , ,
1
1
1 2
2 1
) (
z z
c c D
N
A A AB
A

=
Very dilute soln. x
BM
close to 1
and c constant
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3.Diffusion coefficients for liquids
(several methods)
- unsteady state diffusion in a
long capillary tube- conc. profile

- quasi-steady state diffusion
Diffusion in Liquids
to
c
c c
D N
AB A
'
= =
Where,
c the fraction of area of the
glass open to diffusion
c conc. in the lower chamber
c conc. in the upper chamber
to effective diffusion length
t D
V
A
c c
c c
AB
o
o o
to
c 2
ln
'
'
=

Where,

V
A
to
c 2
- cell constant
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4. Prediction of diffusivities in liquids
(theory for diffusion in liquid is not well established)

Modifying from the Stokes-Einstien equation:
Diffusion in Liquids
3
1
16
10 96 . 9
A
AB
V
T
D

=
By assuming all molecules are alike and arrange in a cubic lattice and
expressing the molecular radius in term of molar volume
Where:
D
AB
: Diffusivity in m2/s
T : Temp.
: viscosity in Pa.s or kg/m.s
V
A
: solute molar volume at its normal boiling point.
4. Prediction of diffusivities in liquids
Modifying from the Stokes-Einstien by Wilke-
Chang:
Diffusion in Liquids
6 . 0
2 / 1 16
) ( 10 173 . 1
A B
B AB
V
T
M D

=
Where:
D
AB
: Diffusivity in m2/s
T : Temp.

B
: viscosity of B in Pa.s or kg/m.s
V
A
: solute molar volume at its normal boiling point.
M
B
: Molecular weight of solvent B
| : an associate parameter of the solvent
Refer example 6.3-2 for your exercise. (p432)
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Mass transfer
Molecular diffusion
Convective mass
transfer
Gases
1. Equimolar counter diffusion in gases
2. General case for diffusion of gases A
and B plus convection
3. Special case for A diffusing through
stagnant, non-diffusing B
4. Diffusion through varying cross-
sectional area
5. Diffusion coefficients for gases
Liquid
Solid

dz
dc
D J
A
AB
Az
*
=
Molar flux of component
A in the z direction:
Bz
*
Az
*
J J =
Equimolar counter diffusion:
) c c ( k N
Li L c A
=
1
Convective mass transfer:
( )
B A
A A
AB A
N N
c
c
dz
dx
cD N + + =
General diffusion & convection
( ) 0 + + =
A
A A
AB A
N
c
c
dz
dx
cD N
Stagnant, non-diffusing B
1
2
1 2 A
A AB
A
p P
p P
ln
) z z ( RT
P D
N

=
( )
2 1
1 2
A A
BM
AB
A
p p
p ) z z ( RT
P D
N

=
Stagnant non-diffusion B,
another form.
4. Diffusion through varying cross-
sectional area
A
N
N
A
A
=
BM
A A AB
A
A
p
P p
RTr
P D
N
r
N
2 1
1
1 2
1
4

= =
t
Sphere
a conduit of non-uniform csa
( )dz P p
dp
RT
D
r
N
N
A
A AB
A
A
/ 1
2

= =
t
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5. Diffusion coefficients for gases
( )
) ( 2
2 1
2 2
A A AB A
BM F F
F
p p P D M
RTp z z
t

=

( )
( )( )
(

+
=

t
V V A / L
V V D
exp
c c
c c
AB
av
av
1 2
2 1
0
2
2
( )
( ) ( ) | |
2
3 / 1 3 / 1
2 / 1 75 . 1 7
/ 1 / 1 10

+
+
=

B A
B A
AB
v v P
M M T
D
AB
Sc
pD
N

=
Stagnant non-diffusion B
The two bulb method
Semi-empirical method of
Fuller et al.
Schmidt number of gases
Liquid








Solid

1 2
2 1
1 2
2 1
) ( ) (
z z
x x c D
z z
c c D
N
A A av AB A A AB
A

=
t D
V
A
c c
c c
AB
o
o o
to
c 2
ln
'
'
=

Diffusion in liquid
Diffusion in coefficients liquid
Prediction of diffusion in liquid
6 . 0
2 / 1 16
) ( 10 173 . 1
A B
B AB
V
T
M D

=
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Diffusion in solids
Typical values for diffusivity in gases, liquids
and solids are shown in table.

General range of values of diffusivity:

Gases : 5 X 10
6
~ 1 X 10
-5
m
2
/ sec.
Liquids : 10
6
~10
-9
m
2
/ sec.
Solids : 5 X 10
14
~1 X 10
-10
m
2
/ sec.

Diffusion in solids
Outlines:
1. Types of diffusion in solids
2. Diffusion in solids following Ficks Law
3. Diffusion in porous solids that depend on
structure
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32
Introduction
- Molecular diffusion in solids slower than gases
and liquids;
- Very important in chemical and biological process
e.g. leaching of food, drying thing (timber, salts and
foods), diffusion and catalytic reaction, treatment of
metal in high temp. etc

Types of diffusion in solids
1. Follow Ficks law
2. depend on actual structure and void channels
Diffusion in solids
Diffusion in solids
1.Diffusion in solids following Ficks Law p 441
( )
B A
A A
AB A
N N
c
c
dz
dx
cD N + + =
Using general equation for binary diffusion;
Bulk-flow is small, it is neglected. Also c is assumed constant.

Giving diffusion in solids;

( )
B A
A
N N
c
c
+
dz
dc D
N
A AB
A
=
1 2
2 1
) (
z z
c c D
N
A A AB
A

=
In case of diffusion through cylinder wall of inner
radius r
1
and outer r
2
and length of L;
) / ln(
2
) (
1 2
2 1
r r
L
c c D N
A A AB A
t
=
6/4/2013
33
2. Diffusion in porous solids that depend on structure
Diffusion in solids
) (
) (
) (
) (
1 2
2 1
1 2
2 1
z z RT
p p D
z z
c c D
N
A A AB A A AB
A

=
t t
c
) (
) (
1 2
2 1
z z
c c D
N
A A AB
A

=
t
c
Diffusion of salt in water
at steady state;
Where;
c: open void fraction
t : tortuosity
Diffusion of gases in porous solids;
Mass transfer
Molecular diffusion
Convective mass
transfer
Gases
1. Equimolar counter diffusion in gases
2. General case for diffusion of gases A
and B plus convection
3. Special case for A diffusing through
stagnant, non-diffusing B
4. Diffusion through varying cross-
sectional area
5. Diffusion coefficients for gases

dz
dc
D J
A
AB
Az
*
=
Molar flux of component
A in the z direction:
Bz
*
Az
*
J J =
Equimolar counter diffusion:
) c c ( k N
Li L c A
=
1
Convective mass transfer:
( )
B A
A A
AB A
N N
c
c
dz
dx
cD N + + =
General diffusion & convection
( ) 0 + + =
A
A A
AB A
N
c
c
dz
dx
cD N
Stagnant, non-diffusing B
6/4/2013
34
1
2
1 2 A
A AB
A
p P
p P
ln
) z z ( RT
P D
N

=
( )
2 1
1 2
A A
BM
AB
A
p p
p ) z z ( RT
P D
N

=
Stagnant non-diffusion B,
another form.
4. Diffusion through varying cross-
sectional area
A
N
N
A
A
=
BM
A A AB
A
A
p
P p
RTr
P D
N
r
N
2 1
1
1 2
1
4

= =
t
Sphere
a conduit of non-uniform csa
( )dz P p
dp
RT
D
r
N
N
A
A AB
A
A
/ 1
2

= =
t
5. Diffusion coefficients for gases
( )
) ( 2
2 1
2 2
A A AB A
BM F F
F
p p P D M
RTp z z
t

=

( )
( )( )
(

+
=

t
V V A / L
V V D
exp
c c
c c
AB
av
av
1 2
2 1
0
2
2
( )
( ) ( ) | |
2
3 / 1 3 / 1
2 / 1 75 . 1 7
/ 1 / 1 10

+
+
=

B A
B A
AB
v v P
M M T
D
AB
Sc
pD
N

=
Stagnant non-diffusion B
The two bulb method
Semi-empirical method of
Fuller et al.
Schmidt number of gases
6/4/2013
35
Liquid








Solid

1 2
2 1
1 2
2 1
) ( ) (
z z
x x c D
z z
c c D
N
A A av AB A A AB
A

=
t D
V
A
c c
c c
AB
o
o o
to
c 2
ln
'
'
=

Diffusion in liquid
Diffusion in coefficients liquid
Prediction of diffusion in liquid
6 . 0
2 / 1 16
) ( 10 173 . 1
A B
B AB
V
T
M D

=
1 2
2 1
) (
z z
c c D
N
A A AB
A

=
Diffusion in solids
Problem based learning
) (
) (
) (
) (
1 2
2 1
1 2
2 1
z z RT
p p D
z z
c c D
N
A A AB A A AB
A

=
t t
c
Diffusion in porous solids
Diffusion of liquid
Diffusion of gas