PP-309 Mass Transfer

Course Facilitator: Nadia khan

Lecture of Week 1 & 2

Department of Polymer & Petrochemical Engineering

NED University of Engineering & Technology
Course Outline
 Diffusion in mass transfer

• Mass transfer by Diffusion, mass transfer operations, applications & significance

• Fick’s law, diffusion in dilute and concentrated solutions, steady state molecular diffusion in binary mixtures of
gases, liquids and solids, Eddy diffusion, mass transfer in laminar flow, mass transfer in turbulent flow, Knudson
Diffusion
• Concept of resistance to mass transfer, coefficients of mass transfer and resistance
• Film mass transfer coefficients for the cases of equi-molar counter diffusion and diffusion of one component (A)
in stagnant component (B). Counter current mass transfer and concept of transfer units. Molecular diffusion in
solids, types of diffusion in solids.

 Theories and Correlations

• Convective mass transfer theories (Two film Theory, Penetration Theory, Surface Renewal Theory and Boundary
Layer Theory) ; Dimensional analysis in mass transfer (Schmidt, Sherwood, Stanton and Marshall numbers).
Correlations for mass transfer coefficients: Reynolds-Chilton -Colburn analogies.
• Convection and chemical reaction, diffusion of gases in porous solids and capillaries.

 Application

• Simultaneous mass and heat transfer, air-water system: humidification and dehumidification, evaporative
cooling, drying operations, cooling towers and dryers design and operation.
• Books:
• Coulson and Richardson, “ Chemical Engineering”.
Volume 1 - Fluid Flow, Heat Transfer and Mass
Transfer (6th Edition)

• Coulson and Richardson, “ Chemical Engineering”.

Volume 2 - Particle Technology and Separation
Processes (5th Edition)

• Dutta, B.K., “Principles of Mass transfer and

Separation Processes”. Prentice-Hall of India, New
Delhi, 2007.
Course Learning Outcomes:
PP-309
At the end of the course, the student will be able to:

DEFINE Fick’s law, diffusion in solid, liquid and

gases, modes of diffusion (molecular and eddy),
1 theories of mass transfer (two film, penetration, C1 PLO 1  Assignment
surface renewal , & boundary
layer),humidification and dehumidification.

SOLVE problems related to diffusion in solids,

liquids and gases using correlations (Reynolds-
Chilton -Colburn analogies),dimensionless
2 C3 PLO 2  Test
numbers (Schmidt, Sherwood and Stanton
numbers) and relations for calculating flux, mass
transfer coefficients and rate of diffusion.

DESIGN industrial cooling towers using

3 C5 PLO 3  Test
psychometric chart and energy balance equations.
• What is Mass Transfer?

It is the transport of species from one point to another in

a single phase or from one phase to another ,generally in
the presence of difference in concentration or partial
pressure called the driving force.
• Numerous examples of mass transfer can be found
throughout the biological, chemical, physical and
engineering fields. Biological involvement includes
respiration mechanism and oxygenation of blood,
kidney functions, food and drug assimilation, and so
forth. The absorption of atmospheric oxygen into
blood occurs in the lungs of living beings. The
absorbed oxygen is supplied to the tissues through
blood circulation. The carbon dioxide generated in
blood is pumped back into the lungs, gets desorbed
and then leaves with the exhaled air..
• Underwater plants, fishes and other living
bodies use oxygen dissolved in water. The
concentration of oxygen in natural water is
usually less than that at saturation. As a result,
atmospheric oxygen gets dissolved in the water
of lakes, rivers and oceans. The transport of
oxygen from air to water is a mass transfer
process since it is caused by a concentration
driving force. The larger the departure of a
system from equilibrium, the greater will be the
driving force and hence the higher the rate of
transport
• Examples of engineering applications include
transpiration and film cooling of rocket and jet-
engine exhaust nozzles, the separation of ores
and isotopes. Chemical engineering applications
consist mainly of diffusional transport of some
components within a phase or from one phase to
another as in gas absorption, distillation, liquid-
liquid extraction, adsorption, drying,
crystallization and several other operations.
Mass transfer applications in chemical industries:

Absorption process:
Separation of CO₂ from flue gases

Distillation process:
separation of mixture of ethanol and water into its
components

Extraction:
Separation of mixtures of toluene and water using benzene as
solvent.

Drying
Drying of Pharmaceutical products.
On the basis of foregoing discussion, we may now
define mass transfer as the movement of one or
more component(s) of a phase in molecular scale
either within the phase or to another phase caused
by the concentration gradient, the transfer taking
place in the direction of decreasing concentration.
Classification of Mass transfer
• The rate of mass transfer is directly proportional
to the concentration gradient and inversely
proportional to the resistance offered by the
medium through which the transfer takes place.
Mass transfer operations are broadly classified
into three categories
1.Direct contact of two immiscible or partially
miscible phases
2. Phases separated by membrane
3. Direct contact of miscible phases.
Direct Contact of Two Immiscible or
Partially Miscible Phases
• Lets consider an example of a mixture of air and
ammonia is brought into intimate contact with
water, ammonia passes on to the liquid phase.
As the concentration of ammonia in the liquid
builds up, the transfer of ammonia from liquid
to gas phase starts and increases till the two
rates of transfer become equal and a dynamic
equilibrium is established within the system.
• At equilibrium, there is no net transfer of
ammonia and no further change in its
concentrations in the two phases occurs unless
the operating conditions are changed and a new
set of equilibrium established. At equilibrium,
the concentrations of ammonia in the two
phases will be different, but their chemical
potential will be the same.
Gas/Vapour–Liquid Contact:
• The separation of one or more components of a
gaseous mixture by preferential dissolution in a
liquid (solvent) is called gas absorption. If on the
other hand, the transfer is from liquid phase to gas
phase, the operation is known as stripping or
desorption. The principle involved in both
absorption or stripping is the same, the only
difference being in the direction of transfer. In these
operations, the added solvent or the gas acts as the
separating agent.
• A typical example of gas absorption is the removal of
carbon dioxide from ammonia synthesis gas by
using aqueous ethanolamine solution or carbonate-
bicarbonate solution. The absorbed gas is recovered
by stripping when the solvent gets regenerated and
becomes fit for reuse. Some other examples are the
removal of (i) acetone form air-acetone mixture, (ii)
hydrogen sulphide from flue gas, (iii) carbon dioxide
from air-carbon dioxide mixture, (iv) sulphur
dioxide from the converter gas in sulphuric acid
plant, and so forth.
• If the liquid phase contains only one component
and the gas phase contains two or more
components, the operation is termed
humidification or dehumidification depending
upon the direction of transfer. In the first case,
the liquid is vaporised and passed on to the gas
phase, while in the second case, some vapour is
condensed and passed on to the liquid phase. In
practice, these two terms mostly refer to air-
water system
Gas–Solid Contact :
• Two important applications of gas-solid contact
are drying and adsorption. If a solid moistened
with a volatile liquid is exposed to a relatively
dry gas, the liquid often vaporises and diffuses
into the gas. This operation is called drying or
sometimes desorption. In drying, the liquid in
majority of cases is water, the drying gas being
air
• Two important applications of gas-solid contact
are drying and adsorption. If a solid moistened
with a volatile liquid is exposed to a relatively
dry gas, the liquid often vaporises and diffuses
into the gas. This operation is called drying or
sometimes desorption. In drying, the liquid in
majority of cases is water, the drying gas being
air
Liquid–Liquid Contact:
if the constituents of a liquid solution are separated by
bringing the solution into intimate contact with
another liquid which is either insoluble or only
partially soluble with the original solution and in
which the constituents of the original solution are
differentially distributed, then the operation is called
liquid-liquid extraction or simply liquid extraction. If
a dilute aqueous solution of acetic acid is brought into
intimate contact with ethyl acetate, the acetic acid and
only a small amount of water enter the ester layer
from which the acetic acid may be easily recovered by
simple distillation.
Liquid–Solid Contact :
The important operations in this category are
leaching, crystallization and adsorption. The selective
dissolution of one or more component(s) from a solid
mixture by a liquid solvent is known as leaching or
solvent extraction. Leaching is widely used in
metallurgical industries for the concentration of metal
bearing minerals or ores. The leaching of gold from its
ore by cyanide solution, the extraction of cotton seed
oil from the seeds by hexane or other suitable solvents
Phases Separated by Membrane
Membranes, in general, prevent intermingling of two
miscible phases and separate the components by
selectively allowing some of them to pass from one
side to the other. In gaseous diffusion or effusion, the
membranes cause separation by allowing components
of different molecular weights to pass through their
microspores at different rates. In permeation, a gas or
liquid solution is brought into contact with a
nonporous membrane in which one of the
components is preferentially dissolved. After diffusing
to the other side of the membrane, the component is
vaporised into the gas phase.
• The solute and solvent of a solution can be
separated by superimposing a pressure to
oppose the osmotic pressure of the solvent and
to reverse its flow. This is known as reverse
osmosis and it has become a very effective
strategy for desalination of sea water.
Direct Contact of Miscible Phases
The separation of components of a single fluid
through the creation of a concentration gradient
within the fluid by imposing a temperature
gradient in the fluid is known as thermal
diffusion. When a condensable vapour like steam
is allowed to diffuse through a gas mixture to
preferentially remove one of the components
along with it, thus making separation possible, it
is called sweep dif usion.
Types of Mass transfer
• Diffusional Mass transfer
• Convective Mass transfer
Diffusional Mass transfer
• Diffusional mass transfer occurs in the absence of
any macroscopic motion of the medium through
which such transfer takes place. As a result,
diffusional mass transfer is a very slow process. The
movement of moisture within a grain during drying
or the transports of a reactant or a product through
the pores of a catalyst pellet are examples of
diffusional mass transfer. Diffusional mass transfer
occurs in quiescent fluids, in fluids moving in
laminar motion in a direction perpendicular to the
direction of transfer or through microspores of
solids.
Convective Mass transfer
• Convective mass transfer, on the other hand,
occurs through a fluid which is in turbulent
motion or subject to stirring so that bulk motion
of the medium takes place. As a result, the rate
of transfer increases several times. For
increasing the rate of transfer, for reducing the
size of equipment and for minimizing the cost,
most industrial operations are carried out by
convective mass transfer
OR
Mass transfer by convection involves the transport
of material between a boundary surface (such
as solid or liquid surface) and a moving fluid or
between two relatively immiscible, moving fluids.
Diffusion
• The term diffusion (mass transfer) is used to
denote the transference of a component in a
mixture from a region where its concentration is
high to a region where the concentration is
lower. Diffusion process can take place in a gas
or vapour or in a liquid, and it can result from
the random velocities of the molecules
(molecular diffusion) or from the circulating or
eddy currents present in a turbulent fluid (eddy
diffusion).
Diffusion & Osmosis
Mechanism of Mass transfer

• Molecular Diffusion
• Eddy Diffusion

Molecular diffusion:

Transport of molecules from higher concentration region to

a lower concentration in a stagnant medium occurs by
molecular diffusion.

Eddy Diffusion:

Transport of molecules from higher concentration region to

a lower concentration in a turbulent medium occurs by
turbulent/ eddy diffusion.
• The transport of species from a point of higher
concentration to a point of lower concentration
in a medium becomes important if the medium
is stagnant or in laminar motion. But molecular
diffusion does not have a significant role to play
in turbulent region except in a region close to
phase boundary.
Molecular Diffusion:

Rate of molecular diffusion can be increased by:

• Increase in temperature
Increasing temperature results in increasing the molecular
motion therefore molecular diffusion will increase

• Decrease the pressure

Decreasing pressure of the systems results in reduction of
the number of collisions which increases the mean free
path of the molecule & the rate of molecular diffusion will
be more.
Eddy diffusion is faster than
molecular diffusion
Concentration is the driving force for mass transfer

Concentration:
Abundance of constituent per volume of mixture.

• Mass Concentration:
Mass per unit volume of the solution or mixture.
ρi = mass concentration of specie i
ρ = total mass concentration
ρi / ρ = mass fraction of specie i in a solution

• Mole Concentration:
Moles per unit volume of the solution or mixture.
Ci = molar concentration of specie i
C =total molar concentration
Ci / C = mole fraction of specie i in a solution
Velocity:

• Species move with different velocities in a gaseous mixture

or liquid solutions. By velocity we mean both the molecular
velocity in the microscopic scale and the bulk motion. By
bulk motion we mean the motion in a fluid caused by a
pressure difference. A diffusing species moves with a
velocity greater than the average velocity of the medium.

Two types of average velocities with respect to stationary

observer are defined here.
• Mass average velocity
Let us consider a non uniform multi-component
fluid mixture, having bulk motion owing to
pressure difference, within which the different
components are moving with different molecular
velocities as a result of diffusion.
• The mass averaged velocity of any mixture is
the velocities of all the species flowing together, taken
with the consideration of their masses.

Where vi is the linear velocity of the ith species in the

concerned direction. It is not the instantaneous velocity of
a molecule of the component. It is rather a statistical mean
of the velocities of the molecules of the component.
• Molar average velocity
The mass averaged velocity of any mixture is
the velocities of all the species flowing together,
taken with the consideration of their moles.
Flux:
Net rate at which a specie in a solution passes
through a unit area, which is normal to the
direction of diffusion , in unit time.
kg/m².s ,kmol/m².s or lbmol/ft².h
Frames of reference:

For expressing the flux of diffusing species three frame of

reference are commonly defined

There is always an observer who observes the

velocity or flux of the species in a mixture.

• For stationary frame of reference ( stationary with respect

to earth) the observer notes the velocity ui for the ith specie

• For the observer who is seated in a frame of reference with

a mass average -velocity u the observer notes the velocity
ui -u for the ith specie

• For the observer who is seated in a frame of reference with

a molar average velocity U the observer notes the velocity
ui -U for the ith specie
Mass Flux

• Relative to stationary observer ni = ρi ui

• Relative to an observer moving with a mass average
velocity ii = ρi (ui –u )
• Relative to an observer moving with a mole average
velocity ji = ρi (ui –U )

Molar Flux

• Relative to stationary observer Ni = Ci ui

• Relative to an observer moving with a mass average
velocity Ii = Ci (ui –u )
• Relative to an observer moving with a mole average
velocity Ji = Ci (ui –U )
Question No 1
A gas mixture N2 = 5%, H2 = 15 %,NH3 = 76 % and
Ar= 4%) flows through a pipe , 25.4 mm in
diameter, at 4.05 bar total pressure.

If the velocities of the respective components are

0.03 m/s, 0.035 m/s, 0.03 m/s and 0.02 m/s.

Calculate the mass average , molar average &

volume average velocities of the mixture.
Solution
Let us call
1= Nitrogen
2=Hydrogen
3= Ammonia
4=Argon
The molar average velocity is given by
U=(∑Ciui)/C
Which is Ci/C is equal to mole fraction so the
equation becomes
U= y1u1+y2c2+y3c3+y4c4
U= 0.05*0.03+0.15*0.035+0.76*0.03+0.04*0.02
U=0.03m/s
u= (ρ1u1+ρ2u2+ρ3u3+ρ4u4)/ρ
As we know that
Pi
ρi= Mi
RT
P
ρ= M
RT
Dividing the both equations we get
Pi
ρi RT Mi Mi
= P = yi
ρ M M
RT
M=y1M1+y2M2+y3M3+y4M4
M= 0.05*28+0.15*2+0.76*16+0.04*40
M= 16.22

u= ∑(yi*Mi*ui)/M

u= (0.05*28*0.03+0.15*2*0.035+0.76*16*0.03
+0.04*40*0.02)/16.22

u= 0.029m/s Ans.
Question No 2
A gas mixture containing 65% NH3, 8% N2, 24% H2
and 3% Ar is flowing through a pipe 25 mm in
diameter at a total pressure of 4.0 atm.
The velocities of the components are as follows:
NH3 = 0.03 m/s, N2 = 0.03 m/s, H2 = 0.035 m/s
and Ar = 0.02 m/s

Calculate the mass average velocity, the molar

average velocity and the volume average velocity of
the gas mixture.
 Solution
Let us denote the components of the gas by subscripts as
under:
NH3 = 1, N2 = 2, H2 = 3 and Ar =4
the mass average velocity of the mixture is
Or

u = (t1u1 + t2u2 + t3u3 + t4u4)

We know that
ti = Mi and t = M
where,
ti = density of the ith component
t = total density of the gas mixture
Mi = molecular weight of the ith component and
M = average molecular weight of the mixture or
Substituting this in Equation, the expression for mass
average velocity, u, becomes
u =∑ yi*ui*Mi
where, M the average molecular weight of the mixture is
given by
M = y1M1 + y2M2 + y3M3 + y4M4
= ( 0.65)(17) + (0.08)(28) + (0.24)(2) + (0.03)(40) = 14.97
Therefore,
u=
((0.65*14*0.03)+(0.08*28*0.03)+(0.24*2*0.035)+(0.03*4
0*0.02))/14.97
u = 0.029 m/s Ans.
From Equation the molar average velocity of the
mixture is
U = (c1u1 + c2u2 + c3u3 + c4u4 )/C
= y1u1 + y2u2 + y3u3 + y4u4
where yi is the mole fraction of the ith component
in the gas mixture.
Substituting the values, we obtain
U = (0.65)(0.03) + (0.08)(0.03) + (0.24)(0.035) +
(0.03)(0.02)
= 0.0309 m/s Ans.
Volume average velocity = Molar average velocity
= 0.0309 m/s Ans.
Models of Diffusion
Tank 1 containing carbon dioxide is connected by a
long connecting line to tank 2 containing air.
Both tanks of equal volume were sufficiently large.
These were kept at constant temperature and
pressure. On opening the valve the diffusion proceed,
and the concentration of carbon dioxide in tank 2 was
measured at a regular interval of time. The
concentration of carbon dioxide in tank 2 thus
measured was found to vary linearly with time as
shown in Figure 2.1(b). Similar observation was made
elsewhere (Cussler 1997) for different system. In
Fick’s model, the results were correlated as
where, the proportionality constant D is the diffusion
coefficient. The other model assumed the carbon dioxide
flux to be proportional to the gas
concentration.

Carbon dioxide flux = k (carbon dioxide concentration

difference)

where, the proportionality constant k is the mass transfer

coefficient. This is a type of reversible rate constant.
• Both the models have some demerits also. For
instance, the flux may not be proportional to the
concentration difference if the capillary is very thin
or if the gases react. The model based on diffusion
coefficient gives results of more fundamental value
than those obtained using the model based on mass
transfer coefficient. The diffusion model has
distributed parameters for the dependent variable,
i.e. the concentration is allowed to vary with all
independent variables like position and time. In
contrast, the mass transfer model has lumped
parameters like average values.
• Fick’s model is commonly used in basic sciences to
describe diffusion. In the mass transfer coefficient
model, on the other hand the coefficient, k takes
care of several parameters which cannot be directly
measured. Mass transfer coefficient leads to the
development of correlations commonly used in
chemical engineering, chemical kinetics and
medicine. Both the models have striking similarity
with Ohm’s law. The diffusion coefficient is
analogous to the reciprocal of resistivity while mass
transfer coefficient is analogous to the reciprocal of
resistance.
Fick’s Law
According to Fick’s law for one-dimensional
steady-state molecular diffusion, the molar flux of
a component in a frame of reference moving with
the molar average velocity is proportional to the
concentration gradient of the component.
If A diffuses in a binary mixture of A and B, then
according to Fick’s law
Where,
• JA = molar flux
• dCA/dz = concentration gradient
• DAB = proportionality constant/ Diffusion
Coefficient / Diffusivity
Similarities of Fick’s Law with Fourier’s Law of
heat conduction & Newton’s Law of Viscosity

Fourier’s Law of heat conduction:

q= - k dT/dz
Where q = heat flux
k = thermal conductivity(proportionality constant)
dT/dz = temperature gradient

Newton’s Law of Viscosity:

τ z x = - μ d u x / dz
τ z x = momentum flux
μ = Viscosity (proportionality constant)
d u x / dz= velocity gradient
Comparing these three equations, the transport of
a property can generally be expressed as

(Flux of a property) = (-) (Diffusivity of the

property) *(Gradient of concentration of the
property)
Fick’s law for one-dimensional diffusional mass
transport in three different co-ordinates can be
represented as
(i) For one dimensional diffusion in Cartesian co-
ordinate

(ii) For radial diffusion in Cylindrical co-ordinate

(i) For radial diffusion in Spherical co-ordinate

Expression for molar flux in terms of diffusivity

Although the original form of Fick’s law as given in

Equation defines molar flux, JA with respect to a frame
of reference moving with the molar average velocity,
molar flux NA with respect to stationary frame of
reference has been found to be more useful for practical
purposes. NA can be derived from JA in the following
way

Fick’s Law
J A = - D AB dCA/ dz -----------eqn (i)
Molar flux in a stationary frame of reference

J A = C A (uA - U) --------------eqn (ii)

Molar average velocity

U= 1/C(CA uA + CB uB)-------- eqn (iii)
In stationary phase
NA = CA uA
NB = CB uB

• Putting values of NA & NB in above eqn (iii)

U= 1/C(NA + NB)

Comparing eqn (i) & (ii)

- D AB dCA/ dz = C A (uA - U)

Putting the value of U in above eqn

- D AB dCA/ dz = (C A uA - C A U )
- D AB dCA/ dz = N A - C A /C ( NA + NB)
N A = C A /C ( NA + NB) - D AB dCA/ dz
Molar Flux of A in terms of stationary observer

• If CA is very small (dilute solution) then

contribution of bulk flow can be neglected. In such
case we may write this equation as

NA = J A = - D AB dCA/ dz

Bulk Flow – most of the fluid is moving

Diffusing molecules move at a velocity greater
than the molar average velocity
Diffusion Velocity:
The diffusing molecules moves at average velocity
greater than molar average velocity. The relative
velocity of a molecular species with respect to an
observer moving with average molar velocity is also
called diffusion velocity.
V A = u A – U =J A /CA = - D AB /CA dCA/ dz

For gas phase Diffusion:

Use partial pressure instead of concentration gradient
N A = P A /P ( NA + NB) - D AB / RT dPA/ dz

In terms of mole fraction:

N A = yA ( NA + NB) - D AB C dyA / dz
 For an ideal gas mixture mutual
diffusivities are equal
Let us consider a rectangular enclosure filled with
air with top surface hot . Air in contact with top
surface having temperature T1, concentration of any
of the constituents of air is C1 and at bottom it
becomes C2. The temperature of bottom is T2. the
total pressure and the partial pressure of the
constituents are uniform throughout the vessel. If
T1> T2 then C1< C2 , which means that there is
concentration gradient within the vessel but the
question is does Nitrogen diffuses in such cases? No
because there is no difference of mole fraction
between top and bottom surfaces of the vessel.
In order to consider this type of situation we have to
use the equations mentioned below.
Adding equations for A & B
THE END