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1 Mass Transfer0001 PDF
1 Mass Transfer0001 PDF
1-Fundamentals
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 2
Cont….
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 3
Mass Transfer in a Single Phase (Binary Diffusion)
• Where NA is the molar flux of A (moles per unit area per unit
time)
• CA is the concentration of A (moles of A per unit volume),
• DAB is known as the diffusivity or diffusion coefficient for A in B,
and y is distance in the direction of transfer.
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 4
Mass Transfer in a Single Phase (Binary Diffusion)
so
• The condition for the pressure or molar concentration to
remain constant in such a system is that there should be no net
transference of molecules. The process is then referred to as
one of equimolecular counter diffusion
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 6
Mass Transfer in a Single Phase (Binary Diffusion)
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 9
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
If A and B are ideal gases in a mixture, the ideal gas law is given by
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 10
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Properties of binary mixtures
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 11
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Properties of binary mixtures
• where XA and XB are the mole fractions of A and B. Thus for a
system at constant pressure P and constant molar
concentration CT.
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 13
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Equimolecular Counter Diffusion
When the mass transfer rates of the two components are equal
and opposite, the process is said to be one of equimolecular
counter diffusion.
In binary distillation applications in which the molar heats of
vaporization for species A and B are approximately equal, both
species are diffusing, but at equal rates in opposite directions.
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 17
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 18
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Mass transfer through a stationary second component
For the absorption of a soluble gas
A from a mixture with an insoluble
gas B, the respective diffusion rates
are given by:
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 19
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 21
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
As:
On integration:
By definition, CBm, the logarithmic mean of CB1 and CB2 is given by:
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 22
Mass transfer through a stationary second component
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 23
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
For small values of CA, CT — CAi Ξ CT and only the first term in the
series is significant
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 24
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Where
Where
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 25
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Where
It may be noted that all the transfer coefficients here are greater
than those for equimolecular counter diffusion by the factor
(CT/CBm)(= P/PBm), which is an integrated form of the drift factor.
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 26
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Example 10.1
Ammonia gas is diffusing at a constant rate through a layer of
stagnant air 1 mm thick. Conditions are such that the gas
contains 50 per cent by volume ammonia at one boundary of
the stagnant layer. The ammonia diffusing to the other
boundary is quickly absorbed and the concentration is negligible
at that plane. The temperature is 295 K and the pressure
atmospheric, and under these conditions the diffusivity of
ammonia in air is 1.8 x 10-5 m2/s. Estimate the rate of diffusion
of ammonia through the layer.
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 27
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 28
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 29
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Mass transfer velocities
According to Fick's law, a species can have a velocity relative to
the mass or molar-average velocity (called diffusion velocity) only
if gradients in the concentration exist.
In a multicomponent system the various species will normally
move at different velocities; for that reason, an evaluation of a
characteristic velocity for the gas mixture requires the averaging
of the velocities of each species present.
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 30
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Mass transfer velocities
It is convenient to express mass transfer rates in terms of
velocities for the species under consideration where:
which, in the S.I system, has the units
(kmol/m2s)/(kmol/m3) = m/s.
and
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 34
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
General case for gas-phase mass transfer in a binary mixture
Substituting:
Similarly for B:
Thus:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
General case for gas-phase mass transfer in a binary mixture
then:
Thus:
Or:
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 37
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
where JA is a flux in mass per unit area and unit time (kg/m2 s in
S.I units), and CA is a concentration in mass terms, (kg/m3 )
5 November 2016 38
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer in a Single Phase
(Binary Diffusion in Gas Mixtures)
Or:
and:
Thus, the diffusional process does not give rise to equal and
opposite mass fluxes.
5 November 2016 39
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Quiz # 1
Ammonia is absorbed in water from a mixture with air
using a column operating at 1 bar and 295 K. The
resistance to transfer may be regarded as lying entirely
within the gas phase. At a point in the column, the partial
pressure of the ammonia is 7.0 kN/m2. The back pressure
at the water interface is negligible and the resistance to
transfer may be regarded as lying in a stationary gas film
1 mm thick. If the diffusivity of ammonia in air is 236 x
10-5 m2/s, what is the transfer rate per unit area at that
point in the column? How would the rate of transfer be
affected if the ammonia air mixture were compressed to
double the pressure?
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer in a Single Phase
(Diffusion in Liquids)
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer in a Single Phase
(Diffusion in Liquids)
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer in a Single Phase
(Diffusion in Liquids)
For component B:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer in a Single Phase
(Diffusion in Liquids)
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
Theoretical models have been developed to describe mass
transfer between a fluid and an interface
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
The two-film theory
The two-film theory of WHITMAN was the first serious attempt
to represent conditions occurring when material is transferred
from one fluid stream to another
Although it does not closely reproduce the conditions in most
practical equipment, the theory gives expressions which can be
applied to the experimental data which are generally available,
and for that reason it is still extensively used.
In this approach, it is assumed that turbulence dies out at the
interface and that a laminar layer exists in each of the two fluids.
Outside the laminar layer, turbulent eddies supplement the
action caused by the random movement of the molecules, and
the resistance to transfer becomes progressively smaller.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
The two-film theory
AGC and DHF
indicate the
hypothetical
concentration
distributions
L1 and L2:
thicknesses of
the two films
5 November 2016 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan 50
hypothetical concentration profiles near
gas–liquid interface
Mass transfer can only occur along a negative concentration gradient
Case:-1
Here the concentrations in both
the gas and liquid phase diminish
in the positive direction, causing
solute to transfer from the gas to
the liquid phase.
The fact that the interfacial liquid
mole fraction is higher than the
gas concentration is no
impediment.
It is an indication of high gas
solubility, a perfectly normal and
acceptable phenomenon.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
hypothetical concentration profiles near
gas–liquid interface
Case:- 2
The gas-phase concentration here
increases in the positive direction
so that no transfer of solute from
gas to liquid can take place.
Neither can there be any transfer in
the opposite sense, because the
liquid concentration rises in the
negative direction.
Such profiles arise only in cases
when solute is generated by
chemical reaction at the gas–
liquid interface. The product
solute then diffuses from the
interface into the bulk fluids.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
hypothetical concentration profiles near
gas–liquid interface
Case:- 3
This case involves decreasing
concentrations in both phases,
but the decrease is in the
negative direction.
Solute will therefore desorb from
the liquid into the gas phase.
Gas solubility is low because
the interfacial concentrations
are nearly identical.
This is an example of stripping
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
hypothetical concentration profiles near
gas–liquid interface
Case 4:
The flat liquid-phase profile
indicates that the liquid phase
is well stirred and shows no
mass transfer resistance.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
hypothetical concentration profiles near
gas–liquid interface
Case 5:
What was stated for Case 4 applies here as
well, but the transfer this time is from the
gas.
This follows from the fact that gas-phase
concentration decreases in the positive
direction.
The question is now asked whether the
results would still be the same if the gas-
phase profiles had in each case been located
above the liquid-phase counterparts. The
answer is yes; transfer would still take place
as indicated before. The only change would
be in the equilibrium solubility of the gas,
which would now be lower than before.
5 November 2016 55
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
The two-film theory
Equilibrium is assumed to exist at the interface and therefore the
relative positions of the points C and D are determined by the
equilibrium relation between the phases.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
The Penetration Theory
The penetration theory was propounded in 1935 by HlGBlE
He was investigating whether or not a resistance to transfer
existed at the interface when a pure gas was absorbed in a
liquid.
In his experiments, a slug-like bubble of carbon dioxide was
allowed rise through a vertical column of water in a 3 mm
diameter glass tube.
As the bubble rose, the displaced liquid ran back as a thin film
between the bubble and the tube,
Higbie assumed that each element of surface in this liquid was
exposed to the gas for the time taken for the gas bubble to
pass it; that is for the time given by the quotient of the bubble
length and its velocity.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
The Penetration Theory
The way in which the
concentration gradient builds up
as a result of exposing a liquid,
initially pure, to the action of a
soluble gas is shown in Figure
which is based on Higbie's
calculations.
The percentage saturation of the
liquid is plotted against the
distance from the surface for a
number of exposure times in Penetration of solute into a solvent
arbitrary units.
Initially only the surface layer contains solute and the concentration changes
abruptly from 100 per cent to 0 per cent at the surface. For progressively
longer exposure times the concentration profile develops as shown, until after
an infinite time the whole of the liquid becomes saturated.
5 November 2016 58
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
The Penetration Theory
5 November 2016 59
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
Regular Surface Renewal Theory
• Dankwerts surface renewal theory (1951), represents an
extansion to penetration theory.
• Higbie always presupposed that the contact time between the
phases was the same at all positions in the apparatus.
• Dankwerts went on to suggest that fluid elements which
come into contact with each other, have different residence
times which can be described by a residence time spectrum.
• One has to imagine that mass exchange between two
different materials in the fluid phase takes place in individual
fluid cells.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Mass Transfer across a Phase Boundary
Models for Mass Transfer at a Fluid-fluid Interface
Regular Surface Renewal Theory
• After a certain amount of time an element can be dislodged
from the contact area and be replaced by another one.
• It has been successfully applied in the absorption of gases
from agitated liquids.
• However the fraction of time for surface renewal is equally as
unknown as the contact time in penetration theory, so both
theories are useful for the understanding of mass transfer
processes, often neither is applicable for the calculation of the
quantities involved in mass transfer
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Phase Equilibria
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Single-Component Phase Equilibrium
If there is only a single component in a mixture, there is only a
single possible temperature (at a given pressure) for which phase
equilibrium is possible.
For example, water at standard pressure (1 atm) can only remain in
equilibrium at 100°C.
Below this temperature, all of the water condenses, and above it,
all of the water vaporizes into steam.
At a given temperature, the unique atmospheric pressure at which a
pure liquid boils is called its vapor pressure.
If the atmospheric pressure is higher than the vapor pressure, the
liquid will not boil.
Vapor pressure is strongly temperature-dependent. Water at 100°C
has a vapor pressure of 1 atmosphere, which explains why water on
Earth (which has an atmosphere of about 1 atm) boils at 100°C.
Water at a temperature of 20°C(a typical room temperature) will
only boil at pressures under 0.023 atm, which is its vapor pressure
at that temperature.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Multiple-Component Phase Equilibrium:
Phase Diagrams
In general, chemical engineers are not dealing with single
components; instead they deal with equilibrium of mixtures.
When a mixture begins to boil, the vapor does not, in general,
have the same composition as the liquid. Instead, the substance
with the lower boiling temperature (or higher vapor pressure)
will have a vapor concentration higher than that with the higher
boiling temperature, though both will be present in the vapor.
A similar argument applies when a vapor mixture condenses.
The concentrations of the vapor and liquid when the overall
concentration and one of the temperature or pressure are fixed
can easily be read off of a phase diagram.
In order to read and understand a phase diagram, it is necessary
to understand the concepts of bubble point and dew point for a
mixture.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Bubble Point and Dew Point
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Pxy Diagram
Composition of each component in a 2-phase mixture,
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Txy Diagram
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Txy Diagram
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
VLE phase diagram summary
To summarize, here's the information you can directly garner
from a phase diagram. Many of these can be used for all
types of phase diagrams, not just VLE.
You can use it to tell you what phase(s) you are in at a given
composition, temperature, and/or pressure.
You can use it to tell you what the composition of each phase
will be, if you're in a multiphase region.
You can use it to tell you how much of the original solution is
in each phase, if you're in a multiphase region.
You can use it to gather some properties of the pure materials
from the endpoints (though these are usually the best-known
of all the mixture properties).
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Problems
Ammonia is absorbed in water from a mixture with air
using a column operating at 1 bar and 295 K. The
resistance to transfer may be regarded as lying entirely
within the gas phase. At a point in the column, the
partial pressure of the ammonia is 7.0 kN/m2. The back
pressure at the water interface is negligible and the
resistance to transfer may be regarded as lying in a
stationary gas film 1 mm thick. If the diffusivity of
ammonia in air is 236 x 10-5 m2/s, what is the transfer
rate per unit area at that point in the column?
How would the rate of transfer be affected if the
ammonia air mixture were compressed to double the
pressure?
5 November 2016 72
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Solution
As we know that:
D P
N
/
( PA1 PA2 )
RT ( y2 y1 ) PBm
A
2.36 *105
N '
A
3
*1.036 * 7000 6.97 *10 5
kmol / m 2
s
8314 * 295 *1*10
5 November 2016 73
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Solution
If the pressure is doubled, the driving force is doubled, CT /CBm
is essentially unaltered, and the diffusivity, being inversely
proportional to the pressure , equation 10.6: D α T1.5 /P ) is
halved. The mass transfer rate therefore remains the same.
5 November 2016 74
Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Problem
The diffusivity of the vapor of a volatile liquid in air can be
conveniently determined by Winkelmann's method in which liquid is
contained in a narrow diameter vertical tube, maintained at a
constant temperature, and an air stream is passed over the top of
the tube sufficiently rapidly to ensure that the partial pressure of
the vapor there remains approximately zero. On the assumption
that the vapor is transferred from the surface of the liquid to the air
stream by molecular diffusion alone, calculate the diffusivity of
carbon tetrachloride vapor in air at 321 K and atmospheric pressure
from the experimental data given in Table 10.3.
The vapor pressure of carbon tetrachloride at 321 K is 37.6 kN/m2
and the density of the liquid is 1540 kg/m3. The kilogram molecular
volume may be taken as 22.4 m3.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Molecular Volume:
The molecular volume is the volume in m3 of
one kmol of the material in the form of liquid
at its boiling point, and is a measure of the
volume occupied by the molecules
themselves. It may not always be known,
although an approximate value can be
obtained, for all but simple molecules, by
application of Kopp '.s law of additive volumes.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Experimental determination of Diffusivities
Diffusivities of vapors are most conveniently determined by the
method developed by WlNKELMANN in which liquid is allowed to
evaporate in a vertical glass tube over the top of which a stream of
vapor-free gas is passed, at a rate such that the vapor pressure is
maintained almost at zero (Figure 10.2). If the apparatus is maintained
at a steady temperature, there will be no eddy currents in the vertical
tube and mass transfer will take place from the surface by molecular
diffusion alone. The rate of evaporation can be followed by the rate of
fall of the liquid surface, and since the concentration gradient is
known, the diffusivity can then be calculated.
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
From equation 10.33 the rate of mass transfer is given by:
Hence:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
L0 will not be measured accurately nor is the effective distance for
diffusion, L, at time t. Accurate values of (L — LO) are available,
however, and hence:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
From a plot of t/(L - LO) against
(L — LO) as shown in Figure:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
A gas containing 88% (by volume) CH4 4%
C2H6 5% n-C3H8 and 3% n-C4H10 at
300 K and 500 kPa will be scrubbed by
contact with a nonvolatile oil in a gas
absorber. The objective of the process is
to recover in the liquid effluent as much
as possible of the heavier hydrocarbons
in the feed (see Figure 1.1). Calculate:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
(a) To calculation of the total molar concentration:
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
(c) Calculation of the mass fraction of each component in the gas
mixture from the intermediate results of part (b):
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
A binary gaseous mixture of components A and B at a pressure of
1 bar and temperature of 300 K undergoes steady-state
equimolarcounterdiffusion along a 1-mm-thick diffusion path. At
one end of the path the mole fraction of component A is 70%,
while at the other end it is 20%. Under these conditions, DAB =
0.1 cm2/s.
Calculate the molar flux of component A
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