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Separation process - I

(Mass Transfer)

Classification of mass transfer operation- Direct


contact of two immiscible phases

This category is most important and includes


almost all the mass transfer operations
In a two phase system of several components at
equilibrium, with few exception, compositions of
the two phases are different.
In most cases, neither equilibrium solutions
contain pure component thus leads to partial
separation
Exception evaporation or condensation of salt
solution

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Three states of aggregations permits six possibility of


phase contact
Gas Gas: With a very few exception, all gases are
soluble in each other this category is practically not
realized.
Gas Liquid:
Fractional distillation: all components of the system
distributes between the phases at equilibrium, partial
evaporation of benzene toluene or HAc water system
Gas absorption: Both phases are different in origin, each
having however one comp or gr of comp which distributes
between the phases. Ex. Mixture of (NH3+Air) in contact
with water
Desorption/Stripping
Humidification/ dehumidification

Gas Solid: Classification according to the no. of


components which appear in two phases
Fractional sublimation: Theoretically feasible, but
practically not done because of inconvenience of
handling solid in this manner.
Drying: if a moistened solid is exposed to relatively dry
gas, liquid will move from solid to gas phase.
Adsorption: Mix. of water vap. and air in contact with
activated silica gel
Fractional adsorption: if several components are
adsorbed on the solid, but with different proportion,
partial sep. can be achieved. Ex. mix. of propane &
propylene activated carbon both are adsorbed
but in different extent

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Liquid Liquid:
Extraction: Sep. involving contact of two
immiscible liquid phases. Mix of
(Acetone+H2O)+CCL4 rich phase (CCl4)
containing large amount of acetone and other is
lean phase.
Fractional extraction:
Sol. of (HAc+Acetone) + insoluble mix. of (CCl4+H2O)
shaking & settling two phases, each containing HAc
and Acetone, but in different proportion.
Two liq. phase sol. may be produced from a single
phase sol. by cooling the later below critical sol. temp.
(CST). Two phases will have diff. comp.

Liquid solid:
Fractional crystallization: all constituents are
present in both phases at equilibrium.
Leaching: selective solution of a comp. from solid
mix. by a liq. solvent. Ex. leaching of gold from its
ore by cyanide sol. and of cottonseed oil from
seed by hexane.
Adsorption: Removal of color material which
contaminate impure cane sugar can be removed
by contacting liq. sol. with activated carbon.

Solid solid: not practically realized because


of extremely slow diffusion rate.

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Membrane Separation
Gas Gas:
Gaseous diffusion/ Effusion: Microporous membrane is
used. Doff. comp. of the gas passes through pores by
diffusion, the rate of which depends on molecular weight
Permeation: non-porous membrane solute first dissolve
in the membrane and then diffuses through it. Sep. of He
from natural gas by selective permeation through
flourocarbon polymer membrane.

Gas liquid: Permeation (pervaporization) sep. of


alcohol from water
Liquid liquid: Dialysis, electrodialysis (ED), forward
osmosis, reverse osmosis (RO), nano-filtration (NF),
ultrafiltration (UF), microfiltration (MF)

Basic concept
Equilibrium: There exist for all combination of
phases a condition of zero net interchange of
properties (usually mass or energy, in chem.
eng.)called equilibrium.
Driving force: For all such combination not in
equilibrium, the diff. in conc. of some property
between one in existing condition and one that
would exist at equil. cond. is a driving force
tending to alter the system toward equil. state.

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Flow pattern:
co-current
counter-current

Continuous/ batch operation: it is more


economical to maintain cont. and steady opn.
with min. disturbances and shutdown. Cont. opn.
greater productivity & lower unit cost.
When small quantity of material are to be
processed batch operation
Transient/ unsteady state operation: observed
during start-up or shut-down of cont. opn.

Molecular diffusion in fluid


It is concerned with the movement of individual
molecules through the substance. KT of gas provides a
means of visualizing what occurs.
Diffusion rate is very low. It with T or P
It can be calculated from KT that rate of evaporation of
water into complete vacuum at 25C is 3.3kg/s.m2, but
placing a 0.1mm thick stagnant air layer at 1std. atm.
evaporation rate by 600 times shows importance of
molecular motion in diffusive movement
Example: dissolution of CuSO4 crystal in water, or
KMnO4 in water

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Difference between molecular diffusion and


eddy diffusion
True driving force in molecular diffusion
Concentration difference
Chemical potential

In multi-phase system, each phase is treated


separately and within each phase, driving
force is described in terms of concentration
difference.

Molecular diffusion
Concentration difference or chemical potential
difference

Pressure diffusion
Motion of solute resulting from pressure difference

Thermal diffusion
Motion of a solute due to thermal (temperature)
gradient

Forced diffusion:
Motion of A due to unequal external forces on A and B

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Definition of concentrations, velocities and fluxes


Mass concentration, i
Molar concentration, ci ( = / )
Mass fraction,
= ,
=
Mole fraction, = ,
=
In a diffusing system, different species are moving with
different velocities.

= velocity of i-th species w.r.t. stationery coordinate


system
Then for a mixture of n-species,
Local mass average velocity,

Definition of concentrations, velocities and fluxes

=Mass flux, local rate at which mass pass


=
through a unit CS placed perpendicular to
velocity . This velocity can be measured by
pitot tube.

Molar average velocity,


Note:

=Molar flux

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Definition of concentrations, velocities and fluxes

Diffusive ability of a molecule is related to


diffusion velocity which is related to moving
coordinate axis fixed in the liquid rather than
the stationery axis.

= Diffusion velocity w.r.t. =

= Diffusion velocity w.r.t. =


Example: swimming fish against a flowing
current

Some relationship:

+
+

=1
=1
+

=
=

=
=

+
+
+

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Mass/ Molar flux

Concentrations

Velocities

Similarity between Mass, Heat and Momentum


transfer

General molecular transport equation:


Rate of a transport process =

General equation for molecular diffusion of


Mass, Heat and Momentum transfer:

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Similarity between Mass, Heat and Momentum


transfer
Newtons law of viscosity for constant density
=
Fouriers law of heat conduction for constant

and

=
Ficks law of diffusion for constant total concentration
(c),

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Problem:
O2 (A) is diffusing through CO (AB) under s.s. condition with CO non-diffusing. Total
pressure is 1105 N/m2 and temperature 0oC. The partial pressure of O2 at two planes
2mm apart is respectively 13000 and 6500 N/m2. The diffusivity for the mixture is
1.8710-5 m2/s. Calculate the diffusion flux of O2.
Solution:
Here,
=

= 1.87 10
= 27

= 13000

= 10
,

, = 0.00
=

= 8314

= 87000

.
.

= 6500

93500
=

= 90200

= 2.97 10

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Problem:
Recalculate the diffusion of O2 (A) assuming that non-diffusing gas is a mixture of CH4
(B) and H2 (C) in the volume ratio 2:1. The diffusivities are estimated to be
=
1.86 10

&

Solution:
Here,
= 90200

= 6.99 10

(as per the earlier problem), where i denotes inert.


2
=
= 0.667 & = 1 0.667 = 0.333
2+1
1
= 2.46 10
, =
+

So,
=

= 3.91 10

Problem:
Water at 25oC is flowing in a covered irrigation ditch below ground. Every
30m, there is a vent line 2.5cm inside diameter and 30cm long to the outside
atmosphere at 25oC. There are 10 vents in 300m ditch. The outside air can be
assumed to be dry. Calculate the total evaporation loss of water in kg/day.
Vapor pressure of water at 25oC is 23.76mm Hg and diffusivity of water vapor
through air at 25oC is 0.26 cm2/s.
Problem:
A spherical gas bulb of volume 500cc contains air NH3 mixture in the
volume ratio of 4:1 at 40oC and 1atm pressure. It is exposed to the
atmosphere at the same temperature and pressure through a capillary of
length 5cm and diameter 1.0mm. If this gas bulb is left open as such, find the
ammonia concentration in the bulb after 15 minutes. Given: DAB for air NH3
at 0oC and 1atm pressure is 0.19810-4 m2/s.

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