MASS TRANSFER 1

CLB 20804
MASS TRANSFER
BASIC PRINCIPLES AND APPLICATIONS
CHAPTER 1
Topic Outcomes
At the end of Chapter 1, you should:
Define and explain the basic concept of mass transfer.
Derive Ficks Law equation.
Calculate mass transfer rate based on unimolecular
diffusion and equimolar counterdiffusion.
Explain the Inter phase mass transfer.
Introduction to
Basic Principles of
diffusion and
applications
Principles of Diffusion Ficks Law
Application to
unimolecular diffusion
and equimolar
counterdiffusion
What are in this chapter?
Introduction
Mass transfer refers to mass in transit due to a species
concentration gradient in a mixture.
When a system contains two or more components whose
concentration vary from point to point , there is a natural
tendency for mass to be transferred.
Minimizing the concentration differences within the system
and moving it towards equilibrium.
Principles of Mass transfer



Mass transfer by ordinary molecular diffusion occurs because
of a concentration difference(driving force for transfer).

The mass transfer rate is proportional to the area normal to
the direction of mass transfer. Not to the volume. So, the rate
expressed as a flux.

Mass transfer stops when the concentration is uniform.
Mechanism of mass transfer involves both molecular diffusion
and convection.

Molecular Diffusion
Net transport of molecules from a region of higher concentration to a
region of lower concentration by random molecular motion.

matter wants to "get away" from the other similar matter and go to a
place where there is open space.
A B
A B
Liquids A and B are separated from each other.
Partition removed.
A goes from high concentration of A to low
concentration of A.
B goes from high concentration of B to low
concentration of B.
Molecules of A and B are uniformly distributed
everywhere in the vessel purely due to the
DIFFUSION.
Molecular Diffusion
Example:
Molecular Diffusion

Sprayed air freshener.
drop of liquid dye
Example of Mass Transfer
At the surface of the lung:
Air Blood
Oxygen
Carbon dioxide
High oxygen concentration
Low carbon dioxide concentration
Low oxygen concentration
High carbon dioxide concentration
Properties of Mixtures
Mass transfer always involves mixtures.
Consequently, we must account for the variation of
physical properties which normally exist in a given
system.
In order to understand the future discussions, let
us first consider definitions and relations which
are often used to explain the role of components
within a mixture.
Chemical
Composition
Moles and
Molecular
Weight
Mass and
Mole Fractions
Average
Molecular
Weight
Concentration

Properties of Mixtures
Definitions
Definitions
:
i
C Molar concentration of species i.
( )
3
kmol/m
:
i

Mass density (kg/m

3
) of species i.
:
i
M Molecular weight (kg/kmol) of species i.
i i i
C = M
*
:
i
J
Molar flux of species i due to diffusion.
( )
2
kmol/s m
Transport of i relative to molar average velocity (v*) of mixture.
:
i
N
''
Absolute molar flux of species i.
( )
2
kmol/s m
Transport of i relative to a fixed reference frame.
:
i
j
Mass flux of species i due to diffusion.
( )
2
kg/s m
Transport of i relative to mass-average velocity (v) of mixture.
Transport of i relative to a fixed reference frame.
:
i
x
Mole fraction of species i
( ) / .
i i
x C C =
:
i
m
Mass fraction of species i
( ) / .
i i
m =
Absolute mass flux of species i.
( )
2
kg/s m
:
i
n
''
Concentrations
Molar concentration of species A:(liquids,solids) ,
(gases)



Where is molecular weight of species A.
Mole fraction:


) (
solids) & (liquids
gases
c
c
y
c
c
x
A
A
A
A
=
=
RT
p
V
n
M
c
A A
A
A
A
= = =

A
M
For a gaseous mixture that obeys the ideal gas law,
mole fraction, can be written in terms of
pressures

For gases,

P
p
RT P
RT p
y
A A
A
= =
A
y
Daltons
law
General Ficks Law Equation of diffusion

Ficks Law




dz
dc
D J
A
AB Az
=
*
The basic empirical relation to estimate the rate of molecular
diffussion:
Molar Flux
Units -
mol/(s.m
2
)
Diffusivity
(constant)
Units -cm
2
/s
alternative form
dz
dy
CD J
A
AB A
=
J
A
z
is the molar flux of A by ordinary molecular
diffusion relative to the molar average velocity of the
mixture in positive z direction, D
AB
is the mutual
diffusion coefficient of A in B, and dc
A
/dz is the
c o n c e n t r a t i o n g r a d i e n t o f A, w h i c h i s
negative in the direction of ordinary molecular diffusion.
Check your understanding-Theory of diffusion

Think of the last time that you washed the dishes. You placed the first
greasy plate into the water and the dishwater got a thin film of oil on the
top of it. Assume that there is no oil at the top of the sink yet. Find the
diffusion 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
. Given the diffusivity is 7x10
-7
cm
2
/s.






6.1-1-Geankoplis(413)
Given : D = 7x10
-7
cm
2
/s.
Find : Calculate the flux.


dC = conc. at the top of the sink conc. of oil on the plate.

The concentration at the top of the sink = 0
The concentration of oil on the plate = 0.1 mol/cm3.
dC = 0 0.1 = -0.1 mol/cm3

dx = the depth of the sink = 18 cm
Check your understanding-Theory of diffusion
J = 3.89 x 10
-9
mol / (cm
2.
s)
1.4 Diffusion Through Moving Bulk Fluid
Movement of A is now due to 2 contributions:

Molecular diffusion fluxes :

Fluxes resulting from bulk flow= C
A
V (kg-mole/m3. m/s)
Concentration of A at any point in
the mixture = C
A
(kg-mole/m
3
)
(1)
Consider a bulk fluid of binary mixture A and B moving in the z-direction
as shown, with an average bulk fluid velocity V m/s, as shown in the Figure
below:
1.4.1 Diffusion Through Moving
Bulk Fluid
Molar flux of A :


Similarly for comp. B:


Total molar flux of A and B:


V C J N
B B B
+ =
N N N
B A
= +
V C J N
A A A
+ =
(2)
(3)
(4)
Also, N = C V
Where, C = total molar concentration
V= average molar velocity(m/s)
(5)
Substitute eqn (4) into eqn (5) :
C
N N
V
B A
+
=
(6)
1.4.1 Diffusion Through Moving
Bulk Fluid


Substitute eqn (1) & (6) into eqn (2) for comp. A:
In term mole fraction:



In term concentration

) ( B A A
A
AB
A
N N y
dz
dy
CD N + + =
(7)
N
A
Mass Transfer Relative to a fixed position
J*
Az
Mass Transfer Relative to a mass or molar average velocity
1.5 Steady-State Equimolar Counter-
Diffusion
For binary mixture A and B,
When gas system is closed and are connected by straight tube, and at
constant pressure and temperature.
Molar fluxes A and B are equal, but opposite in direction
Total pressure is constant throughout.




Thus, diffussion flux are also equal but opposite in direction

0 = + =
B A
N N N
Diffusivity, D
AB
= D
BA

(1)
Mass transfer in the connecting tube is equimolar counter
diffusion by molecular
1.5 Steady-State Equimolar Counter-
Diffusion
1.5.1 Steady-State Equimolar Counter-
Diffusion
Refer to eqn diffusion through moving bulk fluid:

in term mole fraction






Integrated at z= z1, cA= cA1 and at z= z2, cA= cA2 to:



after simplify and rearrangement, the equation becomes :























) ( B A A
A
AB
A
N N y
dz
dy
cD N + + =
0
dz
A
dy
D
AB
c J N A A = =
}
=
2
1
A
y
A
y
dz
A
dy
cD
A
J AB
|
.
|

\
|

=
2 1
) ( 1 2
A
C
A
C
D
A
J
z z
AB
1.5.2 Steady-State Equimolar Counter-
Diffusion of Ideal Gas Mixture:
Consider 2-component gas mixture (A and B)
Ideal Gas Law:



P = Total pressure
n = Total moles of gas

Component-A:


Where;
pA = partial pressure of A
nA = moles of A

nRT Pv =
RT n V P A A =
1.5.2 Steady-State Equimolar Counter-
Diffusion of Ideal Gas Mixture:
Concentration of A:

Differentiating with respect to distance z
Replacing into the original Fick's Law



Integrated Eqn(3) over a diffusional path from z
2
to z
1
&

pA1 to PA2

|
.
|

\
|
=
|
.
|

\
|
=
RT
p
V
n
C
A A
A
|
.
|

\
|
|
.
|

\
|
=
|
.
|

\
|
RT dz
dp
dz
dC
A A
1
dz
Dp
RT
D
J
A AB
A
=
(1)
(2)
(3)
(4)
} }
|
.
|

\
|
=
2
1
2
1
.
PA
pA
A
AB
z
z
A
dp
RT
D
dz J
1.5.2 Steady-State Equimolar Counter-
Diffusion of Ideal Gas Mixture:
where :
p
A1
= partial pressure of A at point 1
p
A2
= partial pressure of A at point 2:
(5)
( )
2 1
) ( 1 2
A A
AB
A
p p
z z RT
D
J

=
Rearrange equation:
Diffusion flux for components A




Diffusion flux for component-B


) (
) (
1 2
2 1
z z RT
p p D
J
B B AB
B

=
Steady-State Equimolar Counter-
Diffusion
( )
2 1
) ( 1 2
A A
AB
A
p p
z z RT
D
J

=
Or, In terms of partial pressure
In terms of concentration
|
.
|

\
|

=
2 1
) ( 1 2
A
C
A
C
D
A
J
z z
AB

Ammonia gas (A) diffusing through a uniform tube 0.10 m long
containing N
2
gas (B) at 1.0132x10
5
Pa pressure and 298 K. At point 1,
p
A1
=1.013x10
4
Pa and point p
A2
= 0.507x10
4
Pa. The diffusivity DAB =
0.230 x 10-4 m2/s. R = 8314 m3.Pa/kg-mole.K

(a) Calculate the diffusion flux J
A
at steady-state.
(b) Repeat for calculate the flux J
B
.



Check your understanding
Given:
Total pressure P
T
= 1.0132 x 10
5
Pa
(constant)
Temperature T = 298 K
D
AB
= 0.230 x 10
-4
m2/s
R = 8314 m3.Pa/kg-mole.K
At point 1, pA1 = 1.013 x 10
4
Pa
At point 2, pA2 = 0.507 x 10
4
Pa
Diffusion path = ( z2 - z1 ) = 0.1 m
Component-A is diffusing from Point 1 to Point 2, as its partial
pressure is higher at point 1.
Solution:
) (
) (
1 2
2 1
z z RT
p p D
J
A A AB
A

=
(a) Calculate the diffusion flux J
A
at steady-state.
(b) Calculate the diffussion flux J
B
.
Use the Dalton's Law of partial pressures to determine the partial pressures
of component-B at points 1 and 2:
PT = p
A
+ pB
At point 1:
pB1 = PT - pA1
PB1 = 1.0132 x 10
5
- 1.013 x 10
4
= 91,190 Pa
At point 2:
pB2 = PT - pA2
PB2 = 1.0132 x 10
5
- 0.507 x 10
4
= 96,250 Pa
Component-B is diffusing in the opposite direction to component-A:
from Point 2 to Point 1, as the partial pressure for B at point 2 is higher.

Flux for component-B is the same as the flux for component-A, but
with a negative sign, indicating that it is in the opposite direction.

Calculate the flux of B in A using:
) (
) (
1 2
2 1
z z RT
p p D
J
B B AB
B

=
1.5.2 Steady-State Equimolar Counter-Diffusion of
Ideal Gas Mixture:
Rate of Diffusion= (molar flux) x (Surface area)

= J
A
x S

Where ;
Rate of Diffusion(unit: kmole/s)
J
A
= Diffusion flux of component A (kmole/m
2 .
s)
S= Surface area(unit m
2
)

1.6 Steady-State One component
Diffusions
Opposite of equimolar counterdiffusion.
One component diffuses, while the other remains stagnant
(nonmoving).
Fig 1.6, point 0 is saturated with component A.
while a stream of pure B flows past the end of the tube removing any A that
has reached point z.
In this situation, the concentration gradient along the tube is exponential
Fig 1.6
1.6 Steady-State One component
Diffusions
Example:
Diffusion of Components liquid benzene (A) through stagnant (nonmoving)
component air (B).
Evaporation of a pure (A) at the bottom of a narrow
tube.
Where a large amount of nondiffussing air (B) is
passed over the top.
Benzene vapor (A) diffuses through the air (B) in the
tube.
Point 1 (Boundary at the liquid surface) ~impermeable
to air (since air is insoluble in benzene liquid).
Hence, air (B) cannot diffuse into or away from the
surface.
Point 2~ partial pressure P
A2
=0(since a large volume of
air is passing by.

Component B cannot diffuse,
N
B
=0
Rearrange eqn (1) to a ficks law form
dz
dy
y
CD
N
A
A
AB
A

=
1
:
(2)
(1)
1.6 Steady-State One component Diffusions
) ( B A A
A
AB
A
N N y
dz
dy
CD N + + =
Refer to equation diffusion through moving bulk fluid



Equation simplifies to


0
) ( A A
A
AB
A
N y
dz
dy
CD N + =
dz
dy
CD N y N
A
AB A A
A
= ) (
1.6 Steady-State One component Diffusions
At quasi steady state condition, rearange eqn becomes in integral form;



Upon integration yields



Log mean (LM) of (1-yA) at the two ends of the stagnants layer :

(
(

=
1
2
1 2
1
1
ln
A
A
AB
y
y
z z
CD
A
N
} }

=
2
1
2
1
1
yA
yA
A
A
A
AB
z
z
y
dy
N
CD
dz
Integration rules
(3)
(4)
( )
( ) | | ) 1 /( 1
1
1 2
1 2
A A
A A
LM A
y y In
y y
y


=
(5)

Rearrange eqn (5)



Subsitute eqn (6)into eqn (4),

( )
( )
( ) | |
( )
( ) | |
( )
( )
LM
A
A A
A
A
Ai A
A Ai
LM
A
Ai A
A
LM
A
y
y y
y
y
In
y y In
y y
y
y y In
yAi y
y

=


=
1 ) 1 (
1
) 1 /( 1
1
) 1 /( 1
) 1 ( 1
1
2 1
1
2
LM A
A A AB
A
y
y y
z z
CD
N
) 1 (
2 1
1 2

=
Finally:
the rate of diffusion is given by (in mole fraction terms)
using the Ideal Gas equation,
|
.
|

\
|
=
|
.
|

\
|
=
RT
p
C
RT
P
C
A
A
(3.1)
General equation Diffusion through moving bulk fluid:



Component B cannot diffuse, NB= 0

) ( B
A
A A
AB
A
N N
C
C
dz
dC
D N + +
|
.
|

\
|
=
(1)
) 0 ( + +
|
.
|

\
|
=
A
A A
AB
A
N
C
C
dz
dC
D N (2)
(3.2)
1.6.2 Steady-State One component Diffusions


Differentiate eqn (3.2) with respect to distance z,



Subsitute eqn (4) and (5) into eqn (2)
A
A A
AB A
N
P
P
dz
dC
D N +
|
.
|

\
|
=
Divide eqn (3.2) with eqn (3.1);
re-arrange:
|
.
|

\
|
|
.
|

\
|
=
dz
dp
RT dz
dC
A A
1
P
p
C
C
A A
=
(

|
.
|

\
|
=
|
.
|

\
|

dz
dp
RT
D
P
p
N
A AB A
A
1
(4)
(5)
(6)
Integrating Eqn (6) from point 1 to point 2: the partial pressure of
A changes from pA1 to pA2 :




Upon integration
} }
|
.
|

\
|

|
.
|

\
|
=
2
1
2
1
1
pA
pA
A
A AB
z
z
A
P
p
dp
RT
D
dz N
Integration rules
(7)
Log mean (LM) of (P-PA) at the two ends of the stagnants
layer :



Rearange eqn (5)


LM
A
A A
AB
A
P P
p P
z z RT
P D
N
,
1
1 2
) (
) (
) (
2

=
( )
( )
( ) | |
( )
( ) | |
( )
( )
LM A
A A
A
A
A A
A A
LM A
A A
A A
LM A
P P
P P
p P
P P
In
P P P P In
P P
P P
P P P P In
P P P P
P P

=


=
2 1
1
2
1 2
2 1
1 2
1 2
) (
) /(
) /(
) (
Subsitute eqn (6)into eqn (4),
Finally:
(9)
(10)
( )
( ) | | ) /(
1 2
2 1
A A
A A
LM A
P P P P In
P P
P P


=
Rate of diffusion is given by (in partial pressure terms)


An open beaker, 6 cm in height, is filled with liquid benzene at 25C to
within 0.5 cm of the top. A gentle breeze of dry air at 25C and 1 atm is
blown by a fan across the mouth of the beaker so that evaporated
benzene is carried away by convection after it transfers through a
stagnant air layer in the beaker. The vapor pressure of benzene at 25C
is 0.131 atm. The mutual diffusion coefficient for benzene in air at 25C
and 1 atm is 0.0905 cm
2
/s. Determine the initial rate of evaporation of
benzene as a molar flux in mol/cm
2
.s
Check your understanding
Evaporation of Benzene from a
beaker
Then
s cm
mol
x N
A
.
10 04 . 1
933 . 0
131 . 0
) 06 . 82 )( 298 ( 5 . 0
0905 . 0
2
6
= =
LM
A
A A
AB
A
P P
p P
z z RT
P D
N
,
1
1 2
) (
) (
) (
2

=
Solution:
Let A = benzene, B = air.

Take Zl = 0.
Then Z
2
- Z
l
= Z = 0.5 cm.

One component equation:
( )
( ) | |
( )
( ) | |
933 . 0
) 131 . 0 1 /( 0 1
131 . 0
) /(
1 2
2 1
=

=


=
In
P P
P P P P In
P P
P P
LM A
A A
A A
LM A
Log mean (LM) of (P-PA) at the two ends of the stagnants layer :
1.7 Diffusion between phases - Phase
Equilibrium

When two immiscible phases are in contact:
Example. gas-liquid, two immiscible liquids, it is possible for
diffusing molecules to pass from one phase to the other across
the interphase boundary.
When diffusion between two phases occurs, there are two
factors to take into account;

1
Equilibrium relationships between the two phases
2
rate at which the diffusion takes place
1.7 Diffusion between phases - Phase
Equilibrium

Referring to Fig 1.7:
If a component, A is passing between phases 1 & 2, there will ultimately be a
dynamic equilibrium established where the rate of diffusion of A is the same in
both directions.
Depending on the type of system (liquid vapour, liquid liquid etc.), the
equilibrium concentration may often be expressed by simple relationships.
Fig 1.7
1.7 Diffusion between phases - Phase
Equilibrium

2 simple relationships are :
Distribution Coefficients






1.6
Where
:

X
A


= concentration of the component A in Phase 1

Y
A
= concentration of the component A in Phase
2

K = constant
Y
A
= KX
A
Henry's Law
1.7 Diffusion between phases - Phase
Equilibrium

Whe
re:
P
A

= Partial pressure of A in the gas phase
C
A

= Concentration of A in the liquid phase
H = constant - called Henry's law constant
Henry's law is a special case of the distribution coefficient for gas-
liquid systems.
In the case of systems where one of the phases is a gas or vapour it
is common to express the concentration in the gas phase terms of
partial pressure.

Thus Henry's Law states that


P
A
= HC
A

1.8 Rate of diffusion between phases -
Mass Transfer
The theory discussed so far enables us to calculate the rates of
diffusion within a single phase and to calculate the concentrations
of a component in two phases when the system is in a state of
equilibrium.

However, many practical problems concern the rate of diffusion
between two phases when the two phases are not in equilibrium.

The rate of mass transfer between two phases is dependant on a
number of factors including:
1. The diffusivity of the diffusing component in the two
phases
2. How far the system is from equilibrium
3. The resistance to transfer across the interface between the
two phases
Mass Transfer Equation
Rate of mass transfer is directly proportional to the driving force for
transfer, and the area available for the transfer process to take place,
that is:
Transfer rate transfer area driving force
The proportional coefficient in this equation is called the mass
transfer
coefficient, so that:
Transfer rate = mass-transfer coefficient
transfer area driving force
1.8 Rate of diffusion between phases -
Mass Transfer
N
A
= kA

C
A
Wher
e:
N
A
= mass transfer rate of A across the
phase boundary

K = mass transfer coefficient
AC = concentration driving force
1.8 Interphase mass transfer
Two-Film Theory of Mass Transfer
In order to illustrate the concept of
interphase mass transfer lets consider
the process of transport of a volatile
chemical across the air/water
interphase.

Gas molecules must diffuse from the
main body of the gas phase to the
gas-liquid interface, then cross this
interface into the liquid side, and
finally diffuses from the interface into
the main body of the liquid.
The concentration driving force is a measure of how far the system
is from equilibrium and may be developed with reference to the
diagram below. (Fig 1.9)
1.9 Concentration driving force
Consider a component, such as oxygen, diffusing from air to water. Assume the
system is at steady state but not at equilibrium.

P
A
= partial pressure of oxygen in the air and C
A
is the concentration of
oxygen in the water.
C
A
*
= concentration of oxygen in water that will be in equilibrium with P
A

P
A*
= partial pressure of oxygen in air that will be in equilibrium with C
A

(Fig 1.9)
1.9 Concentration driving force
The rate of oxygen mass transfer between air and water may be
expressed in two ways.
One based on partial pressure of oxygen in air and one based on the
concentration of oxygen in water.

N
A
= K
G
(P
A
P*
A
)
N
A
= K
L
(C*
A
C
A
)
Wher
e:
P
A

P
A
*

= partial pressure driving force
C
A

C
A
*

= concentration driving force
K
L
= mass transfer coefficient based on the liquid phase.
K
G
= mass transfer coefficient based on the gas phase.

The approriate equilibrium value P
A
* or C
A
* may be calculated using Henry's law
Gas-Liquid Equilibrium Partitioning Curve
C
A,i
P
A,i
P
A

C
A
P
*
A
C
*
A
C
A
P
A

P
A,i
= H C
A,i

P*
A
= H C
A

P
A
= H C*
A

P
A
* = H C
A

P
A
= H C
A
*
What have you learn from this
Chapter?