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Transport Processes

Introduction to Mass Transfer &


Molecular Diffusion

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Introduction to Mass Transfer Operations
The transport or migration of one constituent from a
region of higher concentration to that of a lower
concentration is known as mass transfer.
Mass transfer operations depend on molecules
diffusing from one distinct phase to another and are
based upon differences in the physicochemical
properties of the molecules, such as vapour pressure
or solubility.
For interphase mass transfer, there is a concentration
gradient between bulk and interface, however under
steady state, at interface equilibrium is assumed.
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Introduction to Mass Transfer Operations
A group of operations for separating the components
of mixtures is based on the transfer of material from
one homogeneous phase to another.
These methods is covered by the term mass transfer
operations which include techniques like:
gas absorption and stripping,
liquid-liquid extraction and leaching,
distillation,
Humidification,
drying and crystallization
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PE 311 3
Concentrations & Flux
The concentration of particular species is expressed in
variety of ways. In mass transfer operation, the
concentration gradient is the driving force when other
driving forces (temperature, pressure gradients, etc.)
are kept constant.
The actual driving force for mass transfer to occur is to
create gradient of chemical potential (between two
points) which is a function of all external forces.

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Concentrations & Flux
The concentration gradients are generally
expressed in terms of:
mass concentration of component,
molar concentration of component
mass or mole fraction of species.

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Mass Concentration
Amount of a particular species in a mixture is
defined by the mass of that species per unit
volume, i.e. partial density.
Wi mass of species i in the mixture
i   ...........(1)
V Volume of mixture
The mass density of the mixture itself, , is the
total mass of all species per unit volume;
therefore,
1 W1 W2 Wn
  Wi    ...    i ............(2)
V i V V V
PE 300 - Lecture Series 6
Mass Fraction
The relative amount of species i in the mixture
may be described by the mass of i per unit mass
of the mixture,
mass of species i Wi i V i
mi     ............(3)
mass of mixture Wtot  V 

Equation (3) gives the mass fraction, mi of species


i in the mixture
Leading into:
i
i mi  i   1 0  mi  1.............(4)
PE 300 - Lecture Series 7
Molar Concentration
Expressing the concentration of species i in
the mixture in terms of moles rather than
mass gives:
mass of i Wi
moles of i molecular weight of i M i 1 Wi i
ci      .........(5)
volume V V Mi V Mi
The molar concentration of the mixture, c, is
the total number of moles for all species per
unit volume; thus,
Wi
i moles of i i M i Wi i
c      ci ........(6)
V V i V  Mi i Mi i

PE 300 - Lecture Series 8


Mole Fraction
The mole fraction of species i, xi, is the
number of moles of i per mole of mixture
Wi Wi
moles of i Mi M i V ci
xi     ............(7)
Wi Wi V c
moles of mixture
i M i M
i i

And ci
i xi  i c  1 0  xi  1.................(8)

PE 300 - Lecture Series 9


Molecular Weight
The molecular weight of the mixture is the
number of kg of mixture per kmol of mixture:

M ..........(9)
From Equation (5) and (6) c

   1 1
M     .........(10)
c c 
i
i
i i 1
i M  i M
mi
M i i i i

And from Equation (1) and (2):


Wi
  i i V Wi 1 M i ci
M  i
    M i   xi  M i .........(11)
c c c PE 300i - Lecture
V cM Series
i i c i 10
Mixture compositions and species fluxes
Mole fraction may be converted to mass
fraction using the following relations:
xi  M i xi  M i
mi   ......(12)
M  xk  M k
k

And mi  M mi M i
xi   ...........(13)
Mi  xk / M k
k

The number density, Ni, is given by


Ni  N A  ci ..........(14)
where NA is Avogadro's number, 6.02214 x 1026
molecules/kmol. PE 300 - Lecture Series 11
Ideal gases
Combine the preceding relations with the ideal
gas law.
For any individual component, i, we may write
the partial pressure, Pi, exerted by i as
pi  i  Ri  T ..........(15)
Ro
Where Ri  ..............(16)
Mi
Resulting into
 Ro 
pi  i  Ri  T  M i  ci     T  ci  Ro  T .........(17)
 Mi 
PE 300 - Lecture Series 12
Ideal gases
Giving pi p
c   ci    .........(18)
i i Ro  T Ro  T

Hence Dalton’s law of partial pressures


p   pi ...........(19)
i

ci pi pi
And xi    .........(20)
c c  Ro  T p

PE 300 - Lecture Series 13


Fluxes
The flux is defined as the rate of transport of species i
per unit area in a direction normal to the transport.
The flux is calculated with respect to a fixed reference
frame. The molar flux of species i can be represented
as :

Mass flux is expressed as:

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Fluxes
The units of molar and mass fluxes are moles/m2.s
and mass/m2.s. Sometimes it is convenient to
interpret the total flux of species i with respect to an
arbitrary reference frame rather than a fixed set of
reference frame.
The molar flux of species i based on arbitrary
reference velocity Uo is defined as:
Similarly mass flux of species based on arbitrary
reference velocity Uo is denoted by:

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Example - 1
The most important mixture that we deal with
is air. Its mass composition is: N2 = 0.7556, 02 =
0.2315, Ar = 0.01289, trace gases < 0.01.
Determine xO2, pO2, cO2 and O2 for air at 1 atm.

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Mass Transfer Classification

Mass Transfer

Molecular Convective Mass


Diffusion Transfer

Gases Liquid Solid

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Molecular Diffusion
Molecular diffusion or molecular transport can be
defined as the transfer or movement of individual
molecules through a fluid by means of the random
individual movements of the molecules.
The diffusion of molecules when the whole bulk fluid
is not moving but stationary; the diffusion of
molecules is due to a concentration gradient

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Molecular Diffusion Process

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Fick’s Law of Diffusion
Fick's First Law of Diffusion states that the net
flux of a molecular/mass species A or B is
proportiona1 to the negative gradient of the
concentration of that species, expressed as:
 dx A
J A *  C  DAB  x A  C  DAB  ...........(28)
dx
 dm A
or j A *     DAB  m A     DAB  ...........(29)
dx
For ideal gas
 p 1 dp A
J A*    DAB  x A    DAB  ...........(30)
R T R T dx
PE 300 - Lecture Series 20
Fick’s Law of Diffusion
By comparing the transport laws in
concentration form one sees quantitatively the
molecular-transport analogy
Momentum
du du       d   u  d   u 
            ........(31)
dx dx       dx dx
 Nm  d   u   kg m 1  kg
  3     v 3  v 3
m  dx m s m m s
Nm m3  s m m m3  s m 2
v 3  kg 2 3 
m kg s m kg s
PE 300 - Lecture Series 21
Fick’s Law of Diffusion
Heat
Q    cp  d   c p  T  d   c p  T 
q    
dT
 
dT      ......(32)
A dx dx   c    cp dx dx
 p 

Q  W  d   c p  T  kg J K J
q    2     3  4
A m  dx m kg  K m m
W m4 J 1 m4 m2
 2  
m J s m2 J s
 dC A
J A   DAB ..........(33)
dx
Mass   kg  dC A  kg 1 
J A  2    DAB   DAB  3 
m  s dx m m
 kg  m
4
m2
DAB   2  
 m  s  kg s
PE 300 - Lecture Series 22
Fick’s Law of Diffusion
GASES LIQUIDS
Kinematic viscosity,     [m2/s]
-5
1 to 5 x 10 0.1 to 2 x 10-5
Thermal Diffusivity,      c p [m2/s] 1.5 to 7 x 10- 0.1 to 2 x 10-7
5

Mass Diffusivity, D [m2/s] 0.1 to 5 x 10- 0.1 to 10 x 10-


5 9

Dimensionless Quantities
Kinematic Vis cos ity   c p 0.7 to 1.0 1.0 to 10
Pr andtl number  
Thermal Diffusivity 
Kinematic Vis cos ity  1.0 to 10 10 to 104
Schmidt number  
Mass Diffusivity D
Thermal Diffusivity Schmidt Number  1.0 to 10 102 to 104
Lewis number   
Mass Diffusivity Pr andtl Number D

PE 300 - Lecture Series 23


Example -2
A mixture of He and N2 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 pA1 of He is 0.6 atm and at the other
end 0.2 m pA2 = 0.2 atm. Calculate the flux of He at
steady state if DAB of the He-N2 mixture is 0.687 x 10-4
m2/s.
Convection Mass Transfer
When a fluid flowing outside a solid surface in forced
convection motion, rate of convective mass transfer is given by:

N A  k c (c L1  c Li )
kc - mass transfer coefficient (m/s)
cL1 - bulk fluid conc.
cLi - conc of fluid near the solid surface

Kc depend on:
1. system geometry

2. Fluid properties

3. Flow velocity
Equimolar Counter Diffusion
Consider two gases A and B at constant total pressure
P in two large chamber connected by a tube.

The net moles of A diffusing to the right must be


equal to the net moles of B to the left.

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Example 3
Ammonia gas (A) is diffusing through a uniform
tube 0.10 m long containing N2 gas (B) at 1.0132 x
105 Pa pressure and 298 K. The diagram is similar to
Fig. 6.2-1. At point 1, pA1 = 1.013 x 104 Pa and at point
2, pA2 = 0.507 x 104 Pa. The diffusivity DAB = 0.230 x
10-4 m2/s.
(a) Calculate the flux J*A at steady state
(b) Repeat for J*B
GENERAL CASE FOR DIFFUSION OF GASES A AND
B PLUS CONVECTION
Up to now we have considered Fick's Law of diffusion
in a stationary fluid
There has been no net movement or convective flow of
the entire phase of binary mixture A and B
The diffusion flux occurred because of the
concentration gradient
This flux can be converted to a velocity of diffusion of
A
GENERAL CASE FOR DIFFUSION OF GASES
A AND B PLUS CONVECTION

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For equimolar counterdiffussion, NA=-NB ,
then NA=J*A=-NB=-J*B
Example 4
Water in the bottom of a narrow metal tube is held at a
constant temperature of 293 K. The total pressure of air
(assumed dry) is 1.01325 x 105 Pa (1.0 atm) and the
temperature is 293 K (20 °C). Water evaporates and
diffuses through the air in the tube, and the diffusion
path z2-z1 is 0.1524 m (0.5 ft) long. The diagram is
similar to Fig. 6.2-2a. Calculate the rate of evaporation
at steady state in lb mol/h.ft2 and kg mol/s.m2. The
diffusivity of water vapor at 293 K and 1 am pressure is
0.250 x 10-4 m2/s. Assume that the system is
isothermal. Use SI and English units.
Example 5
A sphere of naphthalene having a radius of 2.0
mm is suspended in a large volume of still air at
318 K and 1.101325 x 105 Pa (1 atm). The
diffusivity of the naphthalene at 318 K is 6.92 x
10-6 m2/s.
Calculate the rate of evaporation of
naphthalene from the surface.
DIFFUSION COEFFICIENTS FOR GASES
Experimental determination of diffusion
coefficients
One method is to evaporate a pure liquid in a
narrow tube with a gas passing over the top
The fall in liquid level is measured with time and
diffusivity calculated
• Experimental diffusivity data
The values range from about
PREDICTION OF DIFFUSIVITY FOR GASES
First prediction using kinetic theory of gases
It is assumed that there are no attractive or
repulsive force between molecules
The derivation uses mean free path, which is the
average distance that a molecules has travelled
between collisions

Where is the mean free path


and average velocity of molecules is
Example 6
Normal butanol (A) is diffusing through air (B)
at 1 atm abs. Using the Fuller et al. method,
estimate the diffusivity DAB for the following
temperatures with the experimental data:
(a) For 0 °C.
(b) For 25.9 °C.
(c) For 0 °C and 2.0 atm abs.
MOLECULAR DIFFUSION IN
LIQUIDS
Diffusion of solutes in liquids is very
important in many industrial processes
especially in such separation as
Liquid-liquid extraction(solvent extraction)
Gas Absorption
Distillation
MOLECULAR DIFFUSION IN LIQUIDS
The rate of molecular diffusion is in liquids is slightly
slower than in gases
Molecules in liquids are very close together compared to
a gas
Molecules of the diffusing solute A will collide with
molecules of liquid B more often
They diffuse more slowly than in gases
The diffusion coefficient in a gas will be of the order of
magnitude of about 100000 times greater than in gas
However the flux in a gas is not that much greater, being
only about 100 times faster
EQUATIONS FOR DIFFUSION IN
LIQUIDS
Equimolar counter diffusion
The equation is similar to that of gas at
steady state
Where
Equimolar counter diffusion
Example 7
Diffusion of A through non diffusing B
This is the most important case of diffusion in liquids
Example is a dilute solution of propionic acid (A) in a
water (B) solution contacted with toluene
Only the propionic acid (A) diffuses through the water
phase to the boundary and to the toluene
The toluene – water interface is a barrier to diffusion of B
and Nb = 0
If gas equation is rewritten in terms of concentrations we
obtain the equation for liquids at steady state
Diffusion of A through non
diffusing B
Example 8
Diffusion in Solids
Rates of diffusion of gases are generally slower than
rates in liquids and gases.
Mass transfer in solids is quite important in chemical
processes such as:
Diffusion and catalytic reaction in solids catalysts
Separation of fluids by membranes
Diffusion of gases through polymer films used in packaging
Treating of metals at high temperatures by gases

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Diffusion in Solids
Transport in solids can be broadly classified into:
Diffusion that follow Fick’s Law ( structure of the solid is not
important)
Diffusion in porous solids (actual structure and void
channels are important)

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STEADY MASS DIFFUSION THROUGH A WALL
Many practical mass transfer problems involve the diffusion of a species through a
plane-parallel medium that does not involve any homogeneous chemical reactions under
one-dimensional steady conditions.

diffusion resistance of
the wall
52
The rate of mass diffusion through a plane wall is
proportional to the average density, the wall area, and the
concentration difference across the wall, but is inversely
proportional to the wall thickness.

molar diffusion resistance of


the wall in s/kmol

53
Steady one-dimensional mass transfer
through nonreacting cylindrical and
spherical layers

On a molar basis

54
Noting that 1 kmol of an ideal gas at the
standard conditions of 0°C and 1 atm
occupies a volume of 22.414 m3, the
volume flow rate of the gas through the
wall by diffusion can be determined
from

55
Example 9

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H/W 2
Discuss the analogy between heat, mass and
momentum transfer

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