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CHG 3111

Unit Operation

Principles of Mass Transfer
Text Book: Chapters 6 & 7

CHG 3111/B. Kruczek
2
Introduction
Basic definitions:

Mass transfer is a rate process that involves net movement of a component in
a mixture from one location to another driven by a concentration gradient.

driving force
rate of a transfer process
resistance
=
Mass transfer versus bulk fluid motion (convective flow)

Bulk fluid motion (e.g. the flow of a fluid through a pipe, or a motion of air induced by a
fan) is not considered as mass transfer
However, mass transfer can be superimposed with bulk fluid flow


Analogy between mass and heat transfer

Mass transfer by diffusion is analogous to conduction heat transfer
Mass transfer by convection is analogous to heat transfer by forced convection


CHG 3111/B. Kruczek
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Steady State Diffusion
Ficks Law of diffusion:

Formulated in 1855 by Fick as an extension of Fouriers law of conduction from
1822.

z
dT
q k
dz
= Fouriers law: where: q
z
, k, T, z are heat flux, thermal conductivity,
temperature, direction of the transport
and = =
* *
A B
Az AB Bz BA
dc dc
J D J D
dz dz
Ficks law (for a binary mixture of A and B):
Molecular diffusion: random-walk process, which
yields a mean-square distance of travel for a given
time interval, but not the direction of travel
Diffusion in the direction of decreasing
concentration (B to left, A to right), but the number
of molecules crossing a given plane in both
direction is the same
CHG 3111/B. Kruczek
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Steady State Diffusion
Equimolar Counterdiffusion in Gasses

Consider two large, well-stirred reservoirs containing ideal mixtures of gases A and B at
constant total pressure connected by a tube where steady state molecular diffusion occurs.

Since the total pressure (P = p
A
+ p
B
) is constant: =
* *
A B
J J
and where: = + =
A B
P
c c c c
RT
Also, since c is constant: ( ) thus: = = = = =
* *
A B A
A B Az AB B BA BA
dc dc dc
dc dc J D J D D
dz dz dz
Consequently: =
AB BA
D D
In addition, partial pressures p
A
and p
B

change linearly with z, thus:
( ) ( )
1 2 1 2
= =

* A A A A AB
A AB
c c p p D
J D
z RT z
where: L is the length of tube
CHG 3111/B. Kruczek
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Steady State Diffusion
General Case: Diffusion of Gases A and B Plus Convection

Consider the case when the whole fluid is moving in bulk (convective flow), but in addition
there is a concentration gradient within the moving fluid

NB 1: Do not confuse
NB 2: The expression for diffusion of gases A and B plus convection holds for diffusion of liquid or solid.
In general,
is the velocity of A relative to a stationary point
bulk velocity
diffusive velocity of A relative to the moving fluid
u
u
u
=
=
=
A
M
Ad
u u u = + .
A Ad M
Multiplying both sides by c
A
: u u u u = + = +
*
A A A Ad A M A A A M
c c c N J c
Since:
u u
+
= = + =
A B
M A B M
N N
N c N N
c
Consequently:
( ) ( ) = + + = + +
A A A
A AB A B A AB A A B
dc c dx
N D N N N cD x N N
dz c dz
To solve the above ordinary differential equation (ODE), the relation between flux N
A
and
N
B
must be known.
For the special case of equimolar counterdiffusion, N
A
= -N
B
, thus:
=
*
A A
N J
with
*
A A
N J
CHG 3111/B. Kruczek
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Steady State Diffusion
Special Case: Diffusion of A through Stagnant, Nondiffusing B
Consider the following physical situation

Evaporation of a pure liquid (A) at the bottom of a narrow tube,
where large amount of inert air (B) is passed over the top of
the tube, i.e., p
A2
= 0
Assuming that air is insoluble in benzene, the liquid surface at
point 1 is impermeable to air; consequently, air is considered
to be stagnant and nondiffusing, i.e., N
B
= 0
Consequently: ( ) 0 = + + = +
A AB A A
A AB A A A A
dx D dp p
N cD x N N N
dz RT dz P
Rearranging and integrating:
2
1
2
1
1
1
| |
= =
} } |

\ .
z pA
A AB A AB A
A A
z pA
A
p D dp D dp
N N dz
P RT dz RT p P ( )
2
2 1 1
| |
=
|

\ .
ln
AB A
A
A
D P P p
N
RT z z P p
Alternatively,
( )
( )
1 2
2 1
=

AB
A A A
BM
D P
N p p
RT z z p
NB: p
MB
is the log mean pressure of inert component B in the tube.
Question: What is the partial pressure profile in the tube, i.e. p
A
= f(z)? How can you determine it?
( )
( )
( ) ( )
( ) ( )
2 1 2 1
2 1 2 1
and
B B A A
BM
B B A A
p p P p P p
p
p p P p P p

= =
(

ln ln
CHG 3111/B. Kruczek
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Steady State Diffusion
Diffusion coefficients for gases
Kinetic theory of gases

Two molecular species A and A* having the same mass and the same size and shape, at low
(near atmospheric) pressures.
If the molecules are rigid and spherical particles (d
A
) and their collisions are completely elastic,
neglecting attractive and repulsion forces, the diffusion coefficient (self diffusion coefficient)
D
AA*
is given by:
Substituting expressions for the molecular speed and mean free path and using ideal gas law to
express n leads to:
( )
1 2
2
23
A

1

3
: = 8 is the mean molecular speed; 1 2 is the mean free path,
in which = N is Boltzmann constant ( =1.38 10 J/
AA
A A
D u
where u T M d n
R

k t t
k k

=
=

*
/
:
A
K) and N is the Avogadro's

number, and is number density n
1 2
3 3 2
3 2
2
3
AA
A A
T
D
M Pd
k
t
| |
=
|
\ .
*
This approach can be extended into the situation when the molecular species are different, i.e.
to a binary mixture of gases A and B
CHG 3111/B. Kruczek
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Steady State Diffusion
Diffusion coefficients for gases
Kinetic theory of gases

More rigorous approach considering intermolecular forces of attraction and repulsion
approximated by Lennard-Jones function
Use of distribution function instead of mean free path (Chapman and Enskog approach).
For a pair of nonpolar molecules A and B:
1 2
7 3 2
2
1 8583 10 1 1
AB
AB D AB A B
T
D
P M M o

| |

= +
|
O
\ . ,
.
where: o
AB
is an average collision diameter, O
D,AB
is a collision integral based on the Lennard-Jones
potential, and D
AB
in [m
2
/s], T in [K], P in [atm], M
A
and M
B
are the molecular weight of A and B in [kg/kmol]
The collision integral (O
D,AB
) is a ratio showing deviation of a gas with interactions compared to a
gas of rigid, elastic spheres (value of 1.0 indicates a gas with no interactions)
Effect of concentrations of A and B on D
AB
is rather weak (less than 4%), and thus can be
neglected.
Prediction of D
AB
from first principles is difficult to apply in practice, because the constants o
AB

and O
D,AB
are rarely available.
CHG 3111/B. Kruczek
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Steady State Diffusion
Diffusion coefficients for gases
Semi-empirical approach method of Fuller

Applicable for mixtures of nonpolar gases or for a polar- nonpolar mixture
( )
( ) ( )
1 2
7 1 75
2
1 3 1 3
1 00 10 1 1
A B
AB
A B
T M M
D
P u u

+
=
(
+

/
.
. / /
and D
AB
in [m
2
/s], T in [K], P in [atm], M
A
and
M
B
in [kg/kmol]
where:
i
is the sum of structural volume increments which can be evaluated from:
CHG 3111/B. Kruczek
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Steady State Diffusion
Diffusion coefficients for gases empirical values at 1 atm
If D
AB
is required at T and P different from those in Table 6.2-2, it can be evaluated using the
correction arising from the Fuller equation, i.e.:
1 75

AB
D T P
.
CHG 3111/B. Kruczek
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Steady State Diffusion
Diffusion coefficients in liquids
Empirical equation of Wilke-Chang
There is no rigorous theory of diffusion in liquids
Unlike the binary gas mixtures, in liquid solution D
AB
depends on concentration of solute in
solvent; in the limiting case of dilute solutions:
( )
1 2
16
0 6
1 713
AB B
B A
T
D M
V
|

=
.
.
where: D
AB
is in [m
2
/s], M
B
are the molecular weight of B in [kg/kmol], T is the absolute temperature in [K],
B
is
the viscosity of B in [Pa s], V
A
is the solute molar volume in [m
3
/kmol], and | is an association parameter of the
solvent, where | is 2.6 for water, 1.9 for methanol, 1.5 for ethanol, 1.0 benzene, ether, heptane and other
unassociated solvents.
If water is the solute, the above equation must be multiplied by 0.435
For high molecular weight solutes (V
A
> 0.5 m
3
/kmol) Stokes-Einstein equation should be used:
16
1 3
9 96 10
AB
A
T
D
V

=
/
.
For low molecular solutes (V
A
< 0.5 m
3
/kmol), the solute molar volume can be can be
determined based on atomic volumes of the atoms of which the molecule is made of, or directly
from a table shown on the next slide.
CHG 3111/B. Kruczek
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Steady State Diffusion
Diffusion coefficients in liquids
Empirical equation of Wilke-Chang
There is no rigorous theory of diffusion in liquids
D
AB
predicted using Wilke-Change equation deviate up to 10 - 15% for aqueous solutions and
up to 25% for non-aqueous solutions
CHG 3111/B. Kruczek
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Steady State Diffusion
Diffusion coefficients for dilute liquids empirical values
Diffusivities in liquids are 4-5 orders
of magnitude lower than viscosities
of gases, but the corresponding
diffusions rates in liquids are only 1-
2 orders of magnitude. Why?
Diffusivities in liquids are practically
independent on the liquid pressure.
Dependence on temperature is
stronger than a direct proportionality,
because the viscosity of liquids is
greatly affected by temperature.
CHG 3111/B. Kruczek
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Steady State Diffusion
Example 1 Equimolar counterdiffusion
Two bulbs A and B of the same volume are connected by a tube of length 5 cm and the
internal diameter of 0.5 cm. Initially, when bulb A contains pure helium while bulb B pure
methane, the molar flow rate of helium from bulb A to bulb B is 4.33 x 10
-6
mol/s. The
temperature and the total pressure in both bulbs are the same and equal to 25
o
C and 1
atm., respectively.

a) What is the initial molar flux of methane from bulb B to bulb A?
b) What is the diffusivity coefficient of helium in methane at the above conditions?
c) What will be the partial pressure of helium in the connecting tube 4 cm from bulb A
when the when the partial pressure of helium in bulb A is 0.8 atm?
d) If the volume of each bulb is 0.001 m
3
, how long will it take for the partial pressure of
helium in bulb A to drop from 1 atm to 0.8 atm?

CHG 3111/B. Kruczek
15
Convective Mass Transfer
Analogy with convective heat transfer
Transfer of a component from a moving fluid to a surface of solid or a surface of another
fluid which is immiscible with the moving fluid.

Question: Is it physically possible for c
i
to be greater than c
Li
? (case in Fig (c) above)?
Moving fluid
Rate equation in convective mass transfer equivalent to Newtons cooling law:
( )
1
where: is a convective mass transfer coefficient =
A c L Li c
N k c c k
Equilibrium distribution coefficient (K) between moving fluid and a surface:

1
=
Li
L
c
K
c
In heat transfer, unless there was a contact resistance, the temperature profile in the system
would be continues
In mass transfer, unless K = 1, the concentration profile have discontinuity
CHG 3111/B. Kruczek
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Convective Mass Transfer
Types of Mass Transfer Coefficients
Mass transfer coefficient for equimolar counterdiffusion (N
A
= -N
B
)

Mass transfer coefficient for A diffusing through stagnant, nondiffusing B (N
B
= 0)

( ) ( ) ( ) ( )
1 2
c c = + + + = + =
'
A A
A AB M A A B AB M A c A A
dx dx
N c D x N N c D N k c c
dz dz
Since the driving force can be expressed not only in terms of concentration difference, the rate
equation can be written in alternative forms:
( ) ( ) ( )
1 2 1 2 1 2
Gases: = = =
' ' '
A c A A G A A y A A
N k c c k p p k y y
( ) ( ) ( )
1 2 1 2 1 2
Liquids: = = =
' ' '
A c A A L A A x A A
N k c c k c c k x x
( )
( )
( ) ( ) ( )
1 2 1 2 1 2
2 1
c +
= = =

'
AB M c
A A A A A c A A
BM BM
D k
N c c c c k c c
z z x x ( )
2 1
2 1
where: and

=
ln
B B
BM
B B
x x
x
x x
=
'
c
c
BM
k
k
x
( ) ( ) ( )
1 2 1 2 1 2
Gases: = = =
A c A A G A A y A A
N k c c k p p k y y
( ) ( ) ( )
1 2 1 2 1 2
Liquids: = = =
A c A A L A A x A A
N k c c k c c k x x
NB: Do not confuse with
'
k k
CHG 3111/B. Kruczek
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Convective Mass Transfer
Summary of Flux Equations and Mass Transfer Coefficients
CHG 3111/B. Kruczek
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Convective Mass Transfer Coefficient
Correlations for mass transfer coefficients
Dimensionless groups to correlated data

Chilton and Colburn J-factor analogy

NB: The properties in dimensionless groups (viscosity and density) are of the flowing mixture, which for
diluted solutions are those of pure fluid B.
Reynolds number: where: is the characteristic length
u

=
Re
L
N L
Question: What are the heat transfer equivalents of Schmidt and Sherwood numbers?
( ) ( )
( )
2 3 2 3
1 3
u
= = = =
' '
/ /
/
Re
....
c G Sh
D Sc Sc
M
Sc
k k P N
J N N
G
N N
Sherwood number: = = = =
'
' '
.....
x
Sh c c BM
AB AB
k
L L
N k k y
D c D
Schmidt number:

=
Sc
AB
N
D
Stanton number: where:
u
u
u
= = = = = =
'
' '
.......
y
c G
St M
M M av
k
k k P
N G c
G G M
Mass transfer coefficient is often correlated as a dimensionless J
D
factor
CHG 3111/B. Kruczek
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Convective Mass Transfer Coefficient
Mass transfer in flows inside pipes

Driving force for mass transfer in internal flows

Laminar flow, i.e.,
( )
( ) ( )
( ) ( )
0
0

=
(

ln
Ai AL Ai A
Ai A
LM
Ai AL Ai A
c c c c
c c
c c c c
Concentration of species A, which being transferred to, or from the moving fluid, can be
assumed constant at the inner surface of the pipe (c
Ai
)
Since the concentration of A in the fluid entering the pipe (c
A0
) is different from c
Ai
, the
concentration of A in the fluid leaving the pipe (c
AL
) must also be different from c
Ai
It can be shown that average driving force for mass transfer of A is given by the log-mean-
concentration difference (c
Ai
c
A
)
LM
2100
u

= <
Re,
:
D
D
N
( )
( )
2 3
0 0668
3 66
1 0 04
(

= = +
+ (

'
Re
Re
.
.
.
Sc
c
Sh
AB
Sc
N N x D
k D
N
D
N N x D
For fully developed flow, i.e. as x/D

3 66 = .
Sh
N :
Turbulent flow:
2100 and 0.5 < < 3000: >
Re,D Sc
N N
( ) ( )
0 83 0 33
0 023 =
. .
Re
.
Sh Sc
N N N For

CHG 3111/B. Kruczek
20
Convective Mass Transfer Coefficient
Correlations for external mass transfer

Mass transfer in flow parallel to flat plates

For 15 000: <
Re,
,
L
N
( ) ( ) ( )
0 5 0 50 0 33
0 664 0 664

= = =
'
. . .
Re, Re,
. .
c
D L Sh L Sc
AB
k L
J N N N N
D
For 15 000 300 000: < <
Re,
, ,
L
N
( ) ( ) ( )
0 2 0 80 0 33
0 036 0 036

= = =
'
. . .
Re, Re,
. .
c
D L Sh L Sc
AB
k L
J N N N N
D
Mass transfer for flow past single spheres
For gases with 1 48 000 and 0 6 2 7 < < < <
Re,
, . . :
D Sc
N N
( ) ( )
0 53 0 33
2 0 552 = +
. .
, Re,
.
Sh D D Sc
N N N
For liquids with 2 2 000: < <
Re,
,
D
N
( ) ( )
0 50 0 33
2 0 95 = +
. .
, Re,
.
Sh D D Sc
N N N
For liquids with 2 000 17 000: < <
Re,
, ,
D
N
( ) ( )
0 62 0 33
2 0 95 = +
. .
, Re,
.
Sh D D Sc
N N N
0 6 2 6 < < . .
Sc
N
Mass transfer for flow past single cylinders
For gases with and liquids with 1 000 3 000 < < , , :
Sc
N ( )
0 487
0 600

=
.
Re,
.
D D
J N
CHG 3111/B. Kruczek
21
Convective Mass Transfer Coefficient
Mass transfer in packed beds

Basic terms an definitions

Void fraction or bed porosity:
Correlations for mass transfer coefficient
u, c
A1

u, c
A2

c, D
p
, a
c
Ai
= const
u =
Re
'
p
N D
Diameter of particles in the bed (D
p
). If bed is made of non-spherical particles,
D
p
is the diameter of sphere having the same surface area as the particle
Specific surface (a) is the total surface area of the total bed volume in [m
2
/m
3
]
and: ( ) 6 1 c =
p
a D
Superficial velocity (u) is the empty bed velocity, which is less than the
actual velocity in the bed (u),
Flow regime is determined by Reynolds number:
u u c = '
( ) c =
total solids total
V V V
The average driving for mass transfer is the
log mean concentration difference:
( )
( ) ( )
( ) ( )
0
0

=
(

ln
Ai AL Ai A
Ai A
LM
Ai AL Ai A
c c c c
c c
c c c c
For liquids in static bed with 00016 55 and 165 70 000 < < < <
Re,
, :
D Sc
N N ( )
2 3
1 09 c

=
/
Re
.
D
J N
For liquids in static bed with 55 1500 and 55 10 690 < < < <
Re,
, , :
D Sc
N N ( )
0 31
0 25 c

=
.
Re
.
D
J N
For static bed with and fluidized bed with 10 10000 < <
Re
N ( )
0 4069
0 4548 c

=
.
Re
.
D
J N 10 4000: < <
Re
N
For liquids in fluidized bed with 1 10 < <
Re,
:
D
N
( )
0 72
1 1068 c

=
.
Re
.
D
J N
CHG 3111/B. Kruczek
22
Convective Mass Transfer Coefficient
Example 2 Laminar and turbulent flow in circular tube

Water at 25
o
C flows at 2 m/s through a straight circular tube cast from benzonic
acid of 1 cm inside diameter. The solubility and diffusivity of benzonic acid in water
are 0.0034 g/cm
3
, and 9.18 x 10
-6
cm
2
/s, respectively, while the water viscosity is
8.9 10
-4
kg/m s.

a) If the water entering the tube has the concentration of benzonic acid of
0.00002 g/cm
3
, what should be the length of the tube for the concentration
at the tube exit of 0.0002 g/cm
3
? What is the corresponding average mass
transfer coefficient?

b) Recalculate the required length of the tube to and the average mass transfer
coefficient if the velocity of water were 0.02 m/s.