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MASS TRANSFER

CHEE 3201
CHAPTER-1

INTRODUCTION
TO MASS TRANSFER
By
MR.C.MARIMUTHU

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MASS
A

measure of how much matter is in an object.

Mass

is commonly measured by how much


something weighs.

But

weight can change depending on where you


are (such as on the moon) while the mass stays
the same.

Mass

is measured in grams, kilograms and, tones


(Metric) and pounds (US units)

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WEIGHT
"Heaviness".

The downward force caused by


gravity on an object.

Even

though weight and mass are different


things, weight often uses the units of mass.

For example
grams, kilograms and, tones (Metric) and
pounds (US units)
1 Kilogram = 2.204 pounds.
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Course Objective
The course should enable the student to
understand the fundamental Principles
and applications of Mass Transfer

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Course Resources
Mass

Transfer Operations By Robert E. Treybal,


McGraw Hill Book Company, Newyork, 3 rd Edition,
1981

Unit

Operations in Chemical Engineering, Mc


Cabe, & Smith, McGraw Hill Book Company, New
york, 7th Ed., 2006

Transport

Processes and Separation Process


Principles, By Geankoplis, C.J., Prentice Hall of
India, New Delhi,2005 4th Edition
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INTRODUCTION
Mass

Transfer Unit Operation


Examples of Mass Transfer
Evaporation of liquid in an open pan
Diffusion of sugar added to coffee
Spreading of blue dye added to
water
Drying of wood and Clothes

Mass Transfer a component


migrates between the same phase
or to a different phase
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INTRODUCTION
Occurrence of Mass Transfer
Concentration Gradient
Ceases at equilibrium
Need for Mass Transfer
Reacting
system
due
to
incomplete conversion
Separation of components from a
mixture
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Types of Mass Transfer


Operations
Mass

Transfer Operations
Depends on type of phases
involved

Phases
Mass
Transfer Operations
Types of
Operations
GasLiquid

Absorption,
Desorption,
Humidification,
Dehumidification, Distillation
Extraction

LiquidLiquid
SolidLeaching,
Liquid/G Desorption,
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as
Crystallization

Adsorption,
Drying,
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Conditions for Mass Transfer

Flow

of Material between phases


Contact between phases
Mass Transfer assisted by
Diffusion
Factors of Mass Transfer
One direction or two direction
motion
Heat and Chemical Reaction
Isothermal and non-Isothermal
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Similarities in M T Operations
Attainment

of equilibrium
Mass transfer both by diffusion
and convection or turbulence
High rate of mass transfer with
high rate of deviation from
equilibrium

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Mass Transfer Operations


Distillation
It

is a Gas-Liquid Operation
Based on Thermal Energy
Depends on difference in volatility i.e.,
difference in vapor pressure
Example:
Separation of Crude into fractions
Separation of heaving boiling
components using steam
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Mass Transfer Operations


Gas Absorption
It

is a gas-liquid Operation
Useful for component separation from a
gaseous mixture
Needs a new Solvent
Separation depends on solubility of component
Example:
Separation of ammonia from ammonia air
mixture
Removal of hydrogen sulphide from
hydrocarbons by alkali solution

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Absorption Column & its


internals

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Mass Transfer Operations


Liquid Extraction
It

is a liquid-liquid operation.
It needs solvent which has preferential
solubility with one of the component.
Commonly used when separation is not
possible by distillation
Example:
Separation of penicillin from fermentation
Separation of acetic acid-water mixture
Separation of dioxane from water-dioxane
mixture
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Extraction Column

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Types of Liquid Extraction Column

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Mass Transfer Operations


Crystallization
It

is a liquid-solid separation
It needs a super saturated solution
and seed crystal
It provides uniform sized particles
from liquid phase

Example:
Sugar crystal from sugar solution
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MASS TRANSFER OPERATIONS


DRYING
It is a gas-solid operation
It is used for remove relatively
small amount of water from solid
material
Example:
Drying of paper pulp

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Spray Drier Equipment

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Basic Terms of Mass Transfer


Expression for Composition
Gram-mole or kg- mole
Weight fraction and Weight %
Mole fraction and Mole %
Partial Pressure

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Basic Terms of Mass


Transfer

Mass flow rate: It is the


quantity of material flow in mass
units per unit time

Molar flow rate: It is the


quantity of material flow in molar
units per unit time.

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Expression of Composition
Gram

mole or kg mole: It is defined as the mass in


(grams or kg) of a substance that is numerically equal to
its molecular weight.

It

is expressed as gram mole or Kilogram mole (kgmole)

Weight

fraction: It is the ratio of the weight of the


individual component to the total weight of the system. It
is denoted by x.

For

two component system, xA+xB = 1.0

Weight%

of A = Weight fraction of A x 100


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Expression of Composition

Mole fraction: It is the ratio of


the
moles
of
individual
component to the total moles of
the system. It is denoted by x.

For a binary system xA + xB =


1.0

Mole% of A = mole fraction of


A x 100
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Expression of
Composition
Partial

Pressure: The partial


pressure of a component gas that
is present in a mixture of gases in
the pressure that would be
exerted by that component if it
alone were present in the same
volume
and
at
the
same
pressure.
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Problems
1.

Calculate the mass concentration


of 2 gram moles of sulphur dioxide
to be used to manufacture sulphuric
acid in a 0.20 m3 of reactor.
2.
A gas mixture has the following
molar
composition 93.5% CH4, 4.6%
C2H6, 1.2%
C3H8 and 0.7% CO2
Calculate (a) Average molecular weight
of the gas mixture (b) weight fraction of
CH4 in the mixture.
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Properties of Gas and Liquids


(Basic Definitions)
Vapour Pressure: It is defined as the
absolute pressure at which the liquid and its
vapor are in equilibrium at a given
temperature.

Ideal Gas Law


Daltons Law
Raoults Law
Henrys Law
Phase Rule
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Ideal Gas Law


It is the law based on Boyle law, Charles law and
Avogadro's hypothesis. It is obeyed by all gases at
low pressures.
Mathematically, an ideal gas law is given by
PV=nRT
Where,
P Pressure (kPa/psi)
V - Volume of gas ( m3/ft3)
N No of moles of gas (kg-mole/lb-mole)
R Universal Gas Constant= 8314Pam 3/kgmole K=
10.73psia ft3/lb mole 0R
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Boyles law
Boyle's

lawis an experimentalgas lawwhich


describes how thepressureof agastends to
decrease as thevolumeof a gas increases.
A modern statement of Boyle's law is

The

absolutepressureexerted by a given mass of an ideal


gasis inversely proportional to thevolumeit occupies if
thetemperatureandamount of gasremain unchanged with in
aclosed system.
Mathematically, Boyle's law can be stated as
P x V= Constant

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Boyles law

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Charles's law
Charles's lawstates that if a
given quantity of gas is held at a
constant pressure, its volume is
directly
proportional
to
the
absolute temperature.

V/T =Constant

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Avagadros hypothesis
Avogadro's

law states that, "equal


volumes of all gases, at the same
temperature and pressure, have the
same number of molecules".

For

a given mass of anideal gas, the


volume and amount (moles) of the
gas are directly proportional if
thetemperatureandpressureare
constant.
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Daltons Law
It states that total pressure of a gas mixture
is equal to partial pressure of gas
components.
Mathematically,
Pt = pA + pB + pc + .
where,
Pt = Total pressure exerted by the gaseous
mixture and pA, pB, pc= partial pressure of
component gases A, B and C
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Raoults Law
It states that the equilibrium pressure
of component A is equal to the
product of the vapor pressure and
mole fraction of A in the liquid phase.
PA = P0A * xA
PA is also related to yA by equation
PA = y A P
yA is the mole fraction of A in the
gas phase.
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Henrys Law
It is applicable for dilute gas liquid
solutions.

It expresses the relationship between


the concentration of gas dissolved in a
liquid and the equilibrium partial pressure
of the gas above the liquid surface.
OR
In other words, the solubility of a gas in
a liquid is directly proportional to the
partial pressure of the gas above the liquid.

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Henrys Law
Mathematically, Henrys law is given as
PA = H x A
Where, H is Henrys law constant.

The Henrys law constant depends


on temperature, solute and solvent.

The concentration of gas dissolved


in a liquid is inversely proportional to
Henrys constant.
Large value of Henrys constant
indicate small concentration of dissolved
gas in liquid.

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Phase Rule
It is the relationship that governs all
heterogeneous equilibrium. It is given
by the relation

F= C-P+2
Where,
C = number of components
P = number of phases &
F= Number of degrees of freedom or
number of intensive variables
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Phase Rule
The degrees of freedom for a system
can
be
temperature,
pressure,
composition that must be specified.
For a system, if degrees of freedom is
fixed, the remaining variables will get
fixed automatically
and makes a
completely defined system.

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Diffusion
It

is the movement of an individual component through a


mixture from a region of higher concentration to a region
of lower concentration at fixed temperature and pressure
with or without the help of external force.

Molecular

Diffusion occurs due to random movement or


motion of molecules.

Molecular

diffusion occurs due to actual migration


of molecules.

As the movement of molecules is faster in gases when


compared to liquid, rate of mass transfer is higher in
gases.
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Diffusion(cont)
The

phenomena of diffusion can be


increased with the help of external forces
i.e., mechanical stirring.

Mechanical

stirring provides convective


movement to the fluid and hence is
called eddy or turbulent diffusion.

The

molecular diffusion is considered as


a slow process compared to eddy
diffusion.
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Diffusion(cont)
The

molecular
diffusion
phenomena is usually considered
to take place in stationary fluid
i.e., fluid at rest and under
laminar flow.

Diffusion

can be altered by
changing the temperature and
pressure
conditions
in
the
system.
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Role of Diffusion in Mass


Transfer
Diffusion

plays an important role in mass transfer.

Diffusion

phenomena can occur either in only one


phase or in both phases of a mass transfer operation.

For

example,

In

distillation, the more volatile component diffuses


through the liquid phase to the interface phase
between the phases (liquid and vapor phases) and
away from the interface into the vapor phase. The
less volatile component diffuses in the opposite
direction and passes from the vapor phase to the
liquid phase.
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Molecular diffusion

A non-uniform mixture tries to attain


uniform concentration by diffusion.

Diffusion phenomena occur as long as a


concentration gradient exists.

Hence, for occurrence of mass transfer


operations, concentration gradient should
exist and mass transfer operation stops as
soon as concentration gradient goes to zero.
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Expression for concentration,


Velocities and Fluxes
Let

us consider a binary system consisting of species A


and B separated by an impermeable partition.

If,

partition is suddenly removed, so that species A will


diffuse into B and species B will diffuse in A and this will
continue till concentration of mixture becomes uniform
everywhere.

In

the above operation the diffusion is only due to


random motion of molecules. In the above condition the
rate of diffusion is governed by Ficks law of diffusion.

Ficks

law of diffusion is applicable for mixture of species


in the same phase i.e., gas in gas, liquid in liquid etc.
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Concentration
There

are various ways to


express the concentration of the
species in a multicomponent
system/mixture. The commonly
used
ways
to
express
concentration or concentration
gradient are mass concentration
and molar concentration.

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Mass concentration:
It

is the mass of species A per unit volume


of the solution (mixture). It is equivalent to
density of A and is designated as A.

For

a binary system, composed of


component A and B,
= A + B
Where,
is the mass density of the solution or
mixture. It is also expressed in other terms
like w and wi also.
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Molar concentration:
It is the number of moles of species A per unit
volume of the solution.
CA = A/MA
Where,
CA = Molar concentration of species A per unit
volume (moles/m3)
A = Mass concentration of species A per unit volume
(mass/m3)
MA = Molecular weight of component A (mass/mole)
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Molar
concentration(cont):
For a binary mixture, total molar
concentration is
C = CA + C B
Where,
C= Total molar concentration (mole/m 3)
CA = Molar concentration of A (mole/m3)
CB = Molar concentration of B (mole/m 3)
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Molar
concentration(cont):
It

is also expressed as c and c i also. For

a
gas
mixture,
to
determine
the
concentration
of species in a gas mixture ideal gas law
relation is used.
The

concentration of component is
expressed in terms of partial pressure.

We

know, For an ideal gas law: PV = nRT


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Molar
concentration(cont):
Similarly for a component A
pAV = nART
OR
CA = nA/V = pA/RT
Where
pA - is the partial pressure of species A in the mixture,
nA- is the number of moles of A in the mixture,
V- is molar volume of the mixture,
T- is the absolute temperature and R is universal gas
constant.

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Molar
concentration(cont):
Rewriting, in terms of mole fraction, xA
XA = CA/C = pA/RT/P/RT = pA/P
Where,
P is the total pressure exerted by the gas mixture.
Total
pressure is also expressed as Pt.
Also, Total concentration, C is
C = CA + CB = pA/RT + pB/RT = P/RT
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Problem
3. A mixture of noble gases (helium, argon,
krypton and xenon) is at a total pressure of
100 kPa and a temperature of 200 K. If the
mixture has equal kmole fractions of each
of the gases,
a) determine Composition of the
mixture in terms of mass fractions.
(b) Total molar concentration of mixture.
(c) Mass density of the mixture .

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Problem
4. Air is stored in a 30 m3 container at 340
K and 101.3 kPa is saturated with water
vapor. Partial pressure of water vapor is
27.35 kPa. Determine the following of the
gas mixture (Molecular Weight of Air =
28.97 and Molecular weight of water=18)
a) Mole fraction of the water vapor
b) Average molecular weight of the mixture
c) Total mass contained in the tank
d) Mass of water vapor in the tank
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Velocities
In

a diffusing mixture, various


chemical species exists and each of
the species have their own mobility.

The

species move with different


velocity due to their difference in
mobility.

Hence, movement of a mixture is


expressed in terms of bulk velocity.
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Velocities(cont)
The

bulk velocity of the mixture is


expressed in terms of average velocity.

In

general, in mass transfer two types of


average velocities are usually used viz.,
local mass average velocity and local
molar average velocity.

The

local mass average velocity is


denoted by u and local molar average
velocity is denoted by U
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Local Mass Average Velocity:


Let us consider a mixture, where
number
of species = n. Let ui be the
velocity of
species
i
with
respect
to
stationary
coordinate system.
Then local
mass average
velocity is given by the relation.
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Local Mass Average


Velocity(cont):
Where,
i = mass concentration of species I
ui = velocity of species I
i = total mass concentration
The term u gives the local rate at which
mass passes through a unit cross-section when
it is placed perpendicular to u.
For a binary system comprising species A and B
u = AuA +BuB/
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Local Molar average Velocity:


Let us consider a mixture, where
number
of species = n. Let ui be the
velocity of
species
i
with
respect
to
stationary
coordinate system.
Then Local
molar
average velocity is given by the
relation
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Local Molar average Velocity


(cont):
The term, Cu is the local rate at
which moles pass through a unit
cross-section which is placed
perpendicular to U.

For

a binary system consisting of


species A and B
U = CAuA+ CBuB/C
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Diffusion Velocity
diffusion velocity of component in
a
mixture can be expressed either in
terms
of mass average velocity or molar
average
velocity.
1. mass diffusion velocity
2. molar diffusion velocity
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Mass Diffusion Velocity


The

mass diffusion velocity of species is the


velocity of the species relative to the local mass
average velocity of the mixture.

i.e.,

Mass diffusion velocity of species i w.r.t. u

u = ui u
For

species A, we can write,

Mass

diffusion of velocity of species A w.r.t.u

u = uA u
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Molar Diffusion Velocity


The

molar diffusion velocity of species is the


velocity of species with respect to relative
to the local molar velocity of the mixture

Molar

diffusion velocity of species i w.r.t.U U


= ui- U

For

Species A, we can write

Molar

diffusion velocity of species A w.r.t. U


U =uA -U
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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
frame of
reference. In mass transfer the flux
can be
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Mass Flux
The

mass flux of a species i is defined as


the mass of the species i that pass
through a unit area per unit time.

The

mass flux relative to the stationary or


fixed coordinates is given by
ni = iui

The

mass flux relative to the mass average


velocity u is given by
Ji = i (ui -u)
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Molar Flux
It

is defined as the moles of species I that


passes through a unit area per unit time.

The

molar flux relative to the stationary


coordinates is given by
Ni= Ci ui

The

molar flux relative to the molar average


velocity U is given by
Ji = Ci (ui-U)
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Expression of Fluxes for a


Binary system
The

various forms of flux for a binary system consisting


component A and B only can be expressed as follows:

Mass

fluxes of A and B relative to stationary coordinates are


nA = A uA
nB = BuB
Mass fluxes of A and B relative to Mass average velocity (u) are
jA = A (uA u)
jB = B (uB u)
Molar fluxes of A and B with respect to stationary co-ordinates
NA = CAuA
NB = CBuB
Molar fluxes of A and B relative Molar average velocity (U) are
JA = CA (uA U)
JB = CB (uB U)
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Inter-relationship with
various types of Fluxes
show that nA = xAni +jA
We know,
nA = AuA
= A (u+uA-u)
= Au + A (uA- u)
= Au + jA

To

We also know, xA = A/ or A = xA
Therefore,
nA = xA(u) +jA
We know,
ni =iui or ni = iui=u
nA = xAni +jA
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Inter-relationship with
various types of Fluxes
To

show that NA = xA(Ni) + JA

We know,
NA = CAuA
=CA (U+uA-U)
= CAU + CA (uA-U)
NA = CAU + JA
We know,
CA =xA C
NA = xACU + JA
We Know,
Ni= Ciui or Ni=CiUi=CU
NA = xA(Ni) + JA
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Ficks law of diffusion

The Ficks law of diffusion of was given by Adolf Fick in 1955.

It provides a relation between the flux of the diffusing


substance and the concentration gradient.

It indicates the rate of mass transfer when molecular


diffusion influences the process.

Ficks law of diffusion states that The flux of diffusing


component A (diffusion flux of A) in z direction in a binary
mixture of A and B is proportional to the molar concentration
gradient.

The proportionality constant is called diffusivity coefficient or


diffusion coefficient.

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Ficks law of
diffusion(cont)

Mathematically,

for one-dimensional steady state diffusion in


a binary mixture, Ficks law is denoted by
JAdCA /dZ
JA = - DABdCA /dZ

Where,
JA Molar flux of A in the direction of Z
CA -Concentration of A ( in moles of A per unit volume)[ kmol/m 3]
dCA/dZ is concentration gradient in the Z-direction
DAB = Molecular diffusivity or diffusion coefficient for component A
diffusing through B.
Z - Distance in the direction of diffusion in m.

The

negative sign indicates diffusion occurs in the direction of


a drop in concentration.
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Diffusivity (DAB)

Diffusivity is defined as the ratio of the flux to the corresponding


concentration gradient.

The SI unit of Diffusivity is m2/s.

The diffusivity of any component is a measure of its diffusive mobility


and is a function of the temperature, pressure, nature and
concentration of the other components.

Diffusive mobility is a function of number of collisions.

Diffusivity increases with decrease in pressure because number of


collisions is less at lower pressure.

However, the effect or pressure is negligible in case of liquids.


Further with increase in temperature diffusivity increases due to
increase in random motion of molecules.
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Three dimensional Molecular


Diffusion
If molecular diffusion occurs in
all the three directions, and
concentration of species in each
direction can be represented in
terms of mole fraction, then
Molar flux is represented by the
relation.

JA = - C DAB (xA/x + xA/y +


xA/z)
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Molecular Diffusion in Gases:


For

a binary mixture, the rate of molecular diffusion or flux


for an ideal gas obeys the relation

JA = DAB (pA1-pA2)/RT (z2-z1)


We know from Ficks law,
JA= -DABdCA/dz
Re arranging and integrating above equation
JA = - DAB
Applying the limit as
at section 1 : Z= Z1, CA = CA1
at section 2 : Z = Z2 CA = CA2

JA = - DAB

JA = DAB (CA!-CA2)/(z2-z1)
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Molecular Diffusion in
Gases(cont):
For

an ideal gas,
PV = nRT
OR
n/V = P/RT = C
Where
n is kgmole of A plus B
V volume in m3
T is temperature in K
R =8314.3 Pa m3/kgmole K
If total pressure P is constant, and c is constant, then c can be expressed
as
C= n/v= p/RT or CA1 = nA1/V= pA1/RT
Hence,
JA = DAB (pA1-pA2)/RT (z2-z1)

It has been found that, for a binary gas mixture the diffusivity coefficient of
A
w.r.t B or diffusivity coefficient of B w.r.t A will be equal. i.e., DAB = DBA
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Problems
1.

2.

3.

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 pipe at point 1 the partial pressure p A1 of He is 0.60 atm and
at the other end 0.2m pA2 = 0.20 atm. Calculate the flux of He
at steady state if DAB of He-N2 mixture is 0.687 x 10-4 m2/s.
A gas of CH4 and He is contained in a tube at 101.32 kPa
pressure and 298 K. At point the partial pressure of methane is
pA1 = 60.72 kPa at a point 0.02 m distance away p A2 = 20.26
kPa. If the total pressure is constant through the tube, calculate
the flux of CH4 (methane) at steady state for equimolar counter
diffusion if DAB of CH4-He mixture is 0.675 x 10-4 m2/s.
Ammonia gas (A) is diffusing through a uniform tube 0.1m m
long containing N2 gas (B) at 1.0132 x 105 Pa and 298 K. At
point 1, pA1 = 1.013 x 104 Pa and at point 2, pA2 = 0.507 x 104
pa. The diffusivity of DAB = 0.230 x 10-4 m2/s. Calculate flux JA
and JB

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Derivation of Expression for Diffusion of Gases A and B along with


convection

We know Ficks law of diffusion is applicable for a stationary


fluid and flux JA occurs due to concentration gradient.

But when whole fluid is moving in bulk, for a stationary


observer, component A is moving faster than the bulk phase,
since diffusion velocity is added to bulk phase velocity.

Hence, the total flux of A will be sum of diffusion flux relative


to moving fluid and convective flux of A relative to the
stationary point.

Hence mathematically, a new relation


NA = -DAB dCA/dz + xA (NA + NB) OR NA = JA +xA (NA+NB)
NA-Convective flux of A
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Derivation of Expression for Diffusion of


Gases A and B along with convection (cont)
For convective diffusion
uA = uAd + uM
uA-Velocity of A relative a stationary point
uAd- diffusion velocity
uM- bulk phase velocity
Multiply with cA
cAuA = cAuAd + cAuM
NA=JA+cAuM
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Derivation of Expression for


Diffusion of Gases A and B along
with convection (cont)

N = cum = NA+NB
um= NA+NB/c
NA = JA+cA/c * (NA+NB)
NA = JA +xA (NA+NB)

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Steady state diffusion of A through a


stagnant gas film or non diffusing B

In

a binary gas mixture, diffusion of A through stagnant or non-diffusing B at


steady state often occurs.

The

above type of diffusion can be observed during evaporation of pure liquid


such as benzene (A) at the bottom of a narrow tube, where large amount of
inert or non-diffusing air (B) is passed over the top.

In

the above case, benzene vapor (A) diffuses through the Air (B) in the tube.

The

boundary at the liquid surface at point 1 is impermeable to air, since air is


insoluble in benzene liquid.

Hence

At

air (B) cannot diffuse into or away from the surface.

point 2 the partial pressure pA2 = 0 since large volume of air is passing by.

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Problem
4.

5.

Water in the bottom of narrow tube is held at constant


temperature of 293 K. The total pressure of air (assumed
dry) is 1.0132 x 105Pa and the temperature is 293 K .
Water evaporates and diffuses through the air in the tube
and the diffusion path z2-z1 is 0.1524 m long. Calculate the
rate of evaporation at steady state in kgmol/m 2.s. The
diffusivity of water vapor at 293 K and 1 atm pressure is
0.250 x 10-4 m2/s. Assume the system is under isothermal
condition.
Methane gas is diffusing in a straight tube 0.1 m long
containing helium at 298 K and a total pressure of 1.01325 x
105 Pa. The partial pressure of CH4 at one end is 1.400 x 104
Pa and 1.33 x 103 Pa at the other end. Helium is insoluble in
one boundary, and hence is non-diffusing or stagnant. The
diffusivity coefficient is 0.675 x10 -4 m2/s. Calculate the flux
of methane in kgmol/m2.s at steady state

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Diffusion through a varying cross section.


In

the earlier cases of diffusion, the cross sectional area


through which diffusion occurs has been constant with
varying distance Z.

But

in some situations, the area A may vary. Then it is


convenient to define NAv = NA/A
Where,
NAv is flux for varying cross section;
NA = flux for constant area
A = cross sectional area.
The diffusion through varying cross section is normally
applied
for (a) Diffusion from a sphere and (b) Diffusion through a
conduit of non-uniform cross-sectional area.
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Expression for diffusion from a


Sphere
The final expression for the
diffusion of A from a sphere is
given by the relation given below:
NAV = NA/4r12 = DAB P/RTr1 *(pA1
A2)/pBM

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Expression for Diffusion through a conduit of non-uniform crosssectional area

In this case, at point 1 the radius is


r1 and at
point 2 radius is r2. At position Z in
the
conduit, for A diffusing through
stagnant,
non-diffusing B,
Taking,
rav =[(r2-r1)/(z2-z1)]z +r1
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Problems
6.

7.

8.

A sphere of naphthalene having a radius of 2.0 mm is suspended in a


large volume of still air at 318 K and 1.01325 x 105 Pa. The surface
temperature of naphthalene can be assumed to abe at 318 K and its
vapour pressure at 318 K is 0.555 mm Hg. The DAB of naphthalene in air
at 318 K is 6.92 x 10-6 m2/s. Calculate the rate of evaporation of
naphthalene from the surface.
Mass transfer is occurring from a sphere of naphthalene having a radius
of 10 mm. The sphere is in a large volume of still air at 52.6 0C and 1
atm abs pressure. The vapor pressure of naphthalene at 52.6 0C is 1.0
mm Hg. The diffusivity of naphthalene in air at 0 0C is 5.16 x 10-6 m2/s.
Calculate the rate of evaporation of naphthalene from the surface in
kgmol/s. m2.
The gas ammonia (A) is diffusing at steady state through N 2 (B) by equimolar counter diffusion in a conduit 1.22 m long at 25 0C and a total
pressure of 101.32 kPa abs. The partial pressure of ammonia at the left
end is 25.33 kPa and 5.066 KPa at the other end. The cross section of
the conduit is in the shape of an equilateral triangle the length of each
side of the triangle being 0.0610 m at the left end and tapering
uniformly to 0.0305 m at the right end. Calculate the molar flux of
ammonia. The diffusivity is DAB = 0.230 x 10-4 m2/s.
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GAS DIFFUSION COEFFICIENT

The diffusion coefficient is a function of temperature,


pressure, nature and concentration of other constituents.

Diffusivity decreases with increase in pressure for


moderate range of pressures upto 25 atm because
number of collisions between species is less at lower
pressure.

The diffusivity increases with increase in temperature


( DAB T1.5) because random thermal movement of
molecule increases with increase in temperature.

The diffusivity is generally higher for gases (in the range


of 0.5 x 10-5 to 1.0 x 106 m2/s).
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Measurement of Gas Phase


Diffusion Coefficient
The gas phase diffusion coefficient can be
determined by experimental methods or by
theoretical relations.
The popular method used to measure
gas diffusivity coefficient is

binary

(I)

evaporation of pure liquid in a narrow tube


with a gas passed over the top, in which the
all in liquid level is measured with time and

(II)

(ii) Twin-bulb method.


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The popular equations used to


predict the
gas phase diffusion coefficient are
Chapman-Enskog equation
2. Fuller et al., equation.
1.

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Chapman-Enskog equation

DAB is the diffusivity in m2/s


T is temperature in K
MA Molecular weight of A in kg mass/kg mol,
MB Molecular weight of B in kgmass/kg mol
P= Absolute pressure in atm.
AB = Average Collision diameter = (A + B)/2
D,AB = Collision integral based on Leonard Jones Potential
The collision integral D,AB is ratio giving the deviation of gas with
interactions compared to gas of rigid, elastic spheres. The value
would be 1.0 for a gas with no interactions. The above equation
predicts diffusivities with an average deviation of about 8% up to
about 1000K. This equation is considered slightly complicated due
to non availability of AB.
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Fueller, Schettler and Giddings equation:

T is temperature in K,
MA, MBare molecular weights of A and B,
P is total pressure in bar and
VA and VB are atomic diffusion volume in
m3.

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Table

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problem
9.

Normal Butanol (A) is diffusing


thorugh air (B) at 1 atm abs.
Using the Fuller et al. method,
estimate the diffusivity DAB for
the following temperatures and
compare with experimental data
for 00C.

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Liquid Diffusion

Diffusion of liquids is very


important in
separation
of
liquid-liquid
extraction, gas
absorption and distillation.

Diffusion in liquids can be seen


in
oxygenation of rivers and lakes
by air and
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Rate

of diffusion in liquids is considerably slower than


gases.

The

moleculaes in a liquid are very close together


compared to gas.

Hence

molecules of the diffusing solute A will collide with


molecules of liquid B more often and diffuse more slowly
than in gases.

Diffusion in liquids can be classified similar to


diffusion in gases as
1.
2.

Diffusion of A through non diffusing B


Equimolar counter diffusion.
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Diffusion of A through non-diffusing B


This represents the most important type of diffusion in liquids. A
good example is separation of dilute solution of propionic acid (A) in
water
(B) solution being contacted with toluene, wherein only propionic acid
diffuses through water phase to boundary and then into toluene phase.
Taking
cav = P/RT and cA1= pA1/RT and xBM=pBM/RT
NA = DABcav/(z2-z1)xBM * (xA1- xA2)
Where,
xBM= xB2-xB1/ln(xB2/xB1)
We know,
xA1+xB1=xA2+xB2=1.0. For dilute solutions, xBM is close to 1.0 and c is
essentially constant. Then above equation simplifies to
NA = DAB (cA1-cA2)/(z2-z1)

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Equimolar counterdiffusion
NA = DAB (cA1-cA2)/ (z2-z1) = DAB*cav* (xA1-xA2)/(z2-z1)

where
NA is the flux of A in kgmol A/s.m2;
DAB-the diffusivity of A in B m2/s;
cA1 is the concentration of A in kgmol A /m3 at point 1;
xA1 mole fraction of A at point 1,
cav = (/M)av = (1/M1+2/M2)/2
Where
cav is the average total concentration of A+B in kgmole/m 3,
M1 is the average molecular weight of the solution at point 1 in kg
mass/kg mol
1 the average density of solution in kg/m3 at point 1

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Problems
10. An

ethanol(A) water (B) solution in the form of stagnant


film 2.0 mm thick at 293 K is in contact at one surface with
an organic solvent in which ethanol is soluble and water is
insoluble. Take NB=0. At point 1 the concentration of
ethanol is 16.8 wt% and solution density is 1 =972.8
kg/m3. At point 2, the concentration of ethanol is 6.8 wt%
and 2 = 988.1 kg/m3. The diffusivity of ethanol is 0.740x
10-9 m2/s. Calculate the steady state flux N A.
11. The solute HCl (A) is diffusing through a thin film of water
(B) 2.0 mm thick at 283 K. The concentration of HCl at
point 1 at one boundary of the film is 12.0 wt% HCl
(density 1 =1060.7 kg/m3) and at the other boundary at
point 2 it is 6.0wt% HCl (2=1030.3 kg/m3). The diffusion
coefficient of HCl in water is 2.5 x10 -9 m2/s. Assuming
steady state and one boundary impermeable to water
calculate flux of HCl in kgmol/s.m 2
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Diffusion in Solids :
The

rate of diffusion in solids is generally slower than


rates in liquids and gases.
In many processes such as drying, adsorption and
membrane separations require the contact of gases
or liquids with solids.
The mechanism of diffusion in solids plays an
important role in many processes such as
heterogeneous catalytic reactions.
The transport in solids by diffusion can be classified
into two types.
1.
2.

Diffusion that can be considered to follow Ficks law


Diffusion in porous solids, where structure and void
channels play an important role.
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Expression for diffusion in


solid which obey Ficks law:
If C is constant, and if diffusion of A through B is constant
and independent of pressure of solids and D AB =DBA then,
Expression for diffusion through solid slab
NA = DAB (CA1-CA2)/z2-z1
Expression for diffusion in radial direction through a
cylinder wall
Assuming the inner radius of cylinder is r1 and outer radius
is r2 and length of cylinder is L
NA= DAB (CA1-CA2) *(2L/ln(r2/r1)
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Expression for diffusion in solid


which obey Ficks law (cont):
The concentration in the solid can be
determined by the relation
CA= SpA/22.414 kgmol A/m3 solid
Where
S is solubility of solute gas (A) in solid.
The units of S is m3 solid per atm partial
pressure of A
pA partial pressure of component A
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Diffusion in porous solids


that depend on Structure :
In diffusion in solids that depend on
structure, the structure of solid and
interaction with the solutes are
important
for the rate of diffusion.

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Expression for Diffusion of


liquids in porous solids:
In

diffusion of liquids in porous solids it is


assumed that solid have pore or interconnected
voids which affect diffusion.

For

case where, voids are completely filled with


liquid water and concentration of salt in water
at boundary 1 is CA1 and at point 2 is CA2.

The

salt in diffusing through the water in the


void volume takes a tortuous path which is
unknown and greater than (z2-z1) by a factor
is called tortuosity.
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Expression for Diffusion of


liquids in porous solids (cont):
Diffusion does not occur in inert solid. For
dilute solution, the expression is
NA = DAB (CA1-CA2)/(z2-z1)
where
is the open void fraction,
DAB is the diffusivity of salt in water
is a factor which corrects for the path longer than
(z2-z1). The value of can vary from about 1.5 to
5.0.
Further,
DAeff = / DAB
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Problem:
12. A

sintered solid of silica 2.0 mm thick


is porous with a void fraction of
0.30 and a tortuosity of 4.0. The
pores are filled with water at 298 K.
At one face the concentration of KCl
is held at 0.10 g mol/liter, and fresh
water flows rapidly by the other face.
Neglecting any other resistances
but that in the porous solid, calculate
the diffusion of KCl at steady state.
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Mass Transfer Coefficient:

In most mass transfer operations, the turbulent flow is


desired to increase the flux or mass transfer rate per unit
area of the equipment.

When turbulent flow occurs, the flow taking place can be


divided into three zones viz., laminar sub-layer, buffer
layer and turbulent flow.

The velocity gradients are more steep in laminar sub-layer.


In such a type of turbulent flow, the mass transfer rate
varies in these zones, it is difficult to predict the rate of mass
transfer in each of the zone and exactly estimate the rate of
the mass transfer in turbulent zone.

From experiments, it has been found that more resistance to


mass transfer exists in laminar sub layer.
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Mass Transfer
Coefficient(cont):
For

all practical purposes, as the


resistance to mass transfer in other three
regions are of low magnitude, all the
resistance to mass transfer is considered
to be exist in laminar sub layer.

This

resistance to mass transfer depends


on thickness of the laminar sub layer.

This

resistance in mass transfer is called


mass transfer coefficient.
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Mass Transfer
Coefficient(cont):
The

flux in these types of mass transfer


operations is denoted by the relation

Flux = mass transfer coefficient x concentration gradient

As concentration can be expressed in different


ways, different types of mass transfer
coefficients are being used to estimate the flux.

Mass

Transfer Coefficient: It is defined as


the rate of mass transfer per unit area per
unit concentration difference.
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Gaseous Phase mass transfer


coefficient:
For gaseous systems again
under turbulent flow conditions,
the diffusion phenomena is found
to obey to mechanisms viz.,
(a)Steady state diffusion of A
through non-diffusing B .
(b)Steady
state
Equimolar
counter diffusion.

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Expression of Steady state diffusion


of A through non-diffusing B

where,

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Expression of Steady state equi-molar counters diffusion of A


and B

where,

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Liquid Phase mass transfer


Coefficient:
In a similar way, when mass transfer
is occurring in liquid phase systems
under turbulent flow conditions, the
diffusion phenomena is found to
follow two mechanisms viz.,
(a) diffusion

of component A through
non-diffusing B

(b) equimolar

counter diffusion.
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Expression for Diffusion of component A through non-diffusing


B :

Or

Where

KL= mass transfer coefficient for liquid


phase for diffusion of A through nondiffusing B.
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Expression for Diffusion of component A


and B under Equimolar counter diffusion:

Where

KL= mass transfer coefficient for


liquid phase.

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Dimensionless Numbers used


in Mass Transfer:
The experimental data for mass transfer coefficients obtained
using various kinds of fluids, different velocities and different
geometries are correlated using dimensionless numbers.
Reynolds Number:
It is defined as ratio of inertia force to viscous force. It
indicates
the degree of turbulence
Re= Inertia force/Viscous force
Re = Du/
Where,
D is the Diameter of pipe (m)
u is the velocity of the fluid (m/s)
is the viscosity of the fluid (Pa.s)
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Schmidt Number(Sc):
It is the ratio of momentum diffusivity to the diffusivity for
mass transfer DAB. It is used to characterize fluid flows in
which there is simultaneous momentum and mass
diffusion by convection process. It physically relates the
relative thickness of the hydrodynamic layer and mass
transfer boundary layer.
Sc = Viscous diffusion rate/ molecular(mass) diffusion rate
Sc=/DAB
where:
is the dynamic viscosity of the fluid (Pas or Ns/m or
kg/ms)
is the density of the fluid (kg/m).
DABis the mass diffusivity (m2/s).
It is analogous to Prandtl number in heat transfer.
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Sherwood Number(Sh):
It is called the mass transfer Nusselt
number. It represents the ratio of
convective to diffusive mass transport.
Sh = Convective mass transfer
coefficient/Diffusive mass transfer
coefficient
Sh= kcL/D
where
L is a characteristic length (m)
D is mass diffusivity (m2.s1)
Kc is the mass transfer coefficient (m.s 1)
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Stanton Number (St):


It is a dimensionless number. In practice, Stanton
number is defined in two different ways viz., in heat
transfer and mass transfer.
In heat transfer it measures the ratio of heat transferred
into a fluid to the thermal capacity of fluid. It is used to
characterize heat transfer in forced convection flows.
St=h/uCp
where
h = convectionheat transfer coefficient
= density of the fluid
cp = specific heat of the fluid
u = speed of the fluid
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Analogies among Heat Mass


and Momentum Transfer:

The mechanism of transfer process


can
be
classified
as
molecular
transport and combined molecular and
eddy transfer.

There are similarities in governing


equation for molecular transport as
well as for turbulent transport. A great
similarity exists between molecular
transport and turbulent transfer.
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We know rate of transport


process depends on driving force
and resistance.
Rate of transfer process = Driving
force/Resistance.

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various analogies:
The various analogies used in
mass transfer are
Reynolds Analogy
2.
Chilton Colburn Analogy
Stanton Number (St):
3.
Taylor Prandtl Analogy
4.
Von Karman Analogy
1.

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Characteristics of Reynolds
analogy:
The assumptions considered are
Only

turbulent core is present


Velocity, temperature and concentration profiles are perfectly
matching.
All diffusivities are same
According

to Reynolds analogy

f/2 = h/Cpu0=kc/u0
Where,
f
= friction factor
h
= Convective heat transfer coefficient
Cp = Specific heat of fluid
uo= velocity of fluid at leading edge
kc= mass transfer coefficient

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Characteristics of Colburn
Analogy:
The assumptions considered are
Only turbulent core is present
Velocity, temperature and concentration
profiles are same
Pr and Sc are not equal to unity

According to Chilton-Colburn analogy


f/2=kc/u0 (Sc)2/3=h/Cpuo * Pr2/3
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Characteristics of TaylorPrandtl Analogy:


Assumptions considered are
Both

turbulent core and laminar


sub layer is present
Pr and Sc are not equal to unity
According to Taylor-Prandtl Analogy
kc/uo=h/Cpuo=(f/2)/[1+5{(f/2)0.5 (Sc-1)]=(f/2)/
[1+5(f/2)0.5(Pr-1)]
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Characteristics of Von
Karman Analogy:
In this analogy, the assumptions considered are
presence

of turbulent core, laminar sub layer


and buffer layer
universal velocity profile equations are
applicable
Pr and Sc are not equal to unity
In this analogy equation obtained is
kc/uo= f/2/{1+5(f/2)0.5[(Sc-1)+ln (5Sc+1)/6)}
kc/uo= f/2/{1+5(f/2)0.5[(Pr-1)+ln(5Pr+1)/6)}
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Mass Transfer for Flow Inside


Pipes:
Laminar Flow
When a liquid or gas is flowing
inside a pipe and the Reynolds
number is < 2100 the flow is said
to be under laminar conditions.
In such a case, mass transfer can
be predicted graphically, using
figure given below.

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Where,
CA is exit concentration
CAo is inlet concentration
CAi concentration at the interface between the wall and gas
The dimensionless W/DABL denotes
W is flow rate in kg/s
L is length of mass transfer section in m.
The above graph is useful for fully developed and parabolic
form of entrance.
On the other hand, for liquids that have small values of DAB,
data follow the parabolic flow line, which is as follows for
W/DABL over 400
CA-CAo/CAi-CAo = 5.5 (W/DABL)-2/3
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Turbulent Flow
For

turbulent flow when


Reynolds number is above 2100,
for gases or liquids flowing inside
a pipe
Sh = 0.023 (Re)0.83 (Sc)0.33
The above equation holds for Sc
of 0.6 to 3000. The Sc for gases
is in the range 0.5-3.0 and for
liquids is above 100 in general.
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Mass Transfer for flow


outside solid surfaces:
Mass Transfer in flow parallel to fluid plate
For

a fluid flow pat a plate in a free stream in an open space


the boundary is not fully developed. For gases or
evaporation of liquids in the gas phase and for laminar flow
(Re=15000) for a flat pate,
JD= 0.064 ReL-0.5
Where ReL = Reynolds number over a flat plate
OR
Sh = 0.0665 ReL0.5 Sc0.33 = kcL/DAB
Where L is the characteristic length in the direction of flow.
For

gases, if ReL is between 15000-300000 then,


JD = 0.99 ReL-0.5
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Mass transfer for flow past


single spheres:
For

flow of gases for Schmidt number


range of 0.6-2.7 and Reynolds number 148000
Sh = 2+ 0.552 Re0.53 Sc0.33
For flow of liquids and Reynolds number
range of 2 to about 2000
Sh = 2+ 0.95 Re0.50 Sc0.33
For liquids and Reynolds number in the
range of 2000-17000 the following
equations are used
Sh = 0.347 Re0.62 Sc0.33
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