MASS TRANSFER OPERATIONS CH2020

Diffusion: diffusion is an important mechanism by which mass transfer happens. A distinguishing feature
of diffusion is that it results in mixing or mass transport without requiring bulk motion.

We visualize matter using two approaches:

The idea of continuum: physical phenomena can be modeled assuming the materials exist as
a Continuum, meaning the matter in the body is continuously distributed and fills the entire
region of space it occupies. A continuum is a body that can be continually sub-divided
into infinitesimal elements with properties being those of the bulk material.
Molecular picture
In this course, our problem formulation will always be based on continuum picture
Balance Equations:
1. Mass Balance: total mass is conserved or mass cannot be created or destroyed.

In rectangular coordinates
2. Linear Momentum balance: The rate of change of momentum is related to overall forces acting
on a body.

In the mass and momentum balance, we have incorporated velocity, u. If the material consists of several
components, we interpret the overall velocity as averaged velocity. A and B are the components in the
mixture, we denote component velocities as UA and UB. (
Mass averaged velocity is

Mass Flux (kg/m2s): Mass flux of a component is the mass being transported per unit area per unit
second (

Molar Flux (mol/m2 s): moles being transported per unit area per unit second [ NA].
Where NA= Molar flux of A, MA= Molecular mass of A, AUA is Mass flux of A.
Flux is a vector and overall fluxes are as follows

For Multicomponent Mixture

Both Mass flux and Molar flux can be related as follows:

Overall flux of A (NA) = Flux of A due to bulk motion (NxA) + Flux of A due to diffusion (JA). If total flux is
N, then the flux of A due to bulk motion would be NXA, where XA is the mole fraction of A. NA = JA + NxA
Therefore Flux due to diffusion of A, where JA is molar flux due to diffusion

Diffusion phenomenon in multicomponent mixtures:

The molar fluxes are related to each other: NA = xAN+ JA, Using this definition, for all components

Average molar velocity: Um is the molar average velocity.

Mass flux due to diffusion ( jA) : The mass flux due to diffusion will be MiJI. Since the molecular weight of
different species will be different, summation of MiJI
. However, we could define all the fluxes on
mass basis, such that:

Where

density and u is component velocity. Based on this we can see that:

The diffusion flux, on the mass basis, is defined in terms of Ficks law as:

Rewriting the diffusion fluxes in terms of the difference of component motion and the bulk motion,

Clearly JA will be involved in component balance, and we will have to make hypotheses to calculate JA
1. Ficks law: Simplest approach to define migration of species, which is based on analogy to heat
conduction
The problems associated with its use
Diffusivities are very strong functions of composition / concentration.

Multicomponent diffusivities may not be related to the binary diffusivities.

we predominantly use the first approach (Ficks law) which uses concentration gradient as a
mechanism

There are other methods to analyze transport of components in a a mixture relative to other
components:
Stefan-Maxwell equations
Kinetic theory, Chapman-Enskong procedure:
Irreversible thermodynamics
Mechanical theory of diffusion:
Component balance: The rate of change of mass of a component is equal fluxes due to diffusion. In
addition, a component can also appear/disappear due to chemical reactions.

In rectangular coordinates -

For a constant density solution this will simplify to ( A=MACA)

Idea of mass transfer coefficient comes from the following expressionThe relationship between wall stress (interfacial stress, interface between Solid and fluid) and friction
factor could be

This equation is interpreted as follows:

The momentum driving force = momentum of the fluid - momentum of solid (pipe,plate etc) =
( uo 0)
The momentum flux transferred between fluid and solid = wall stress = I
The momentum transfer coefficient = fuo/2

In mass transfer also similar approach is used : Let us say that we are interested in mass transfer of
component A in a liquid phase to liquid phase interface. Then, analogous to Eq. 33, we write the mass
flux to be related to:
NA = KL(CA,i CAo) . Where CA,i and CA,o are the concentration of A at the interface and bulk liquid,
respectively.
Next diffusion coefficients in various systems will be discussed, we know that motion and arrangement
of molecules is very different in gases, in liquids, in solids and in polymers. Therefore, analysis of
diffusion depends on which molecule is diffusing, and in what substance/s. Since molecules are
understood to be involved in myriad interactions and random motions, a random walker is a good way
of describing motion of a molecule. The description of random walk problems will give us insights into
diffusion phenomenon.
Random Walk: A random walk is the process by which randomly-moving objects wander away
from where they started. The figure shows 7 black dots that start in one place randomly walking away

We assume,
one - dimensional random walker, walking in x -direction.
starts from the origin, and has an equal probability of taking a step in +x or -x direction.
each step is of uniform size l
If the walker takes n steps, the number of ways he walker can take m steps in +X direction(and
therefore, n-m steps in -x direction) is
This is a binomial distribution

The average position of the random walker will be at the origin:

Lets assume black dot takes n steps and d is the total distance travelled by
black dot , it can be either positive or negative. d= a1+a2+a3+a4+..an
average=
. But
as a1 has an equal probability of
+1 or -1, we assume average value is 0. Therefore the average position will be at origin. This did not give
any idea of how far the black dot gets after n steps.

The average distance traveled is related to the step size and the total number of steps ( nl2 ) : Even
though d can be positive or negative, d2 is always positive. <d2> = <(a1 + a2 + a3 + ... + aN)2> = <(a1 + a2 +
a3 + ... + aN) (a1 + a2 + a3 + ... + aN)> = (<a12> + <a22> + <a32> + ... + <aN2>) + 2 (<a1a2> + <a1a3> + ... <a1aN> +
<a2a3> + ... <a2aN> + .)
If the step size is l, a1 can either be +l or l. either way, a12 =l2. Then on average a12 is l2 and <a12> = l2.
Since a1a2 is equally likely to be +1 or -1, <a1a2> = 0. Therefore <d2> = nl2
The larger the number of steps, the longer time is taken by the random walker.
Distance traveled is proportional to square root of time.
Probability of finding the random walker at a distance between x and x+dx is given by, 2 is a measure of
the spread of the Gaussian distribution, and is directly proportional
to < x2 >

The step size depends on how much can a molecule travel before colliding with other molecule/s, or
how does molecule interact with other molecules which is predominantly different in gases, liquids ,
solids and polymers. We can qualitatively state that rate of diffusion would be higher if the step size of
diffusing molecules.
A diffusion coefficient can be defined based on the mean square displacement of a random walker,

Mean square displacement and diffusion coefficient in gases: The starting point for understanding
diffusivity in gases is from kinetic theory. There are no interactions in an ideal gas; the displacement is
just related to velocity and time. Therefore, mean square displacement is proportional to 2. We will
consider gas molecules as hard spheres (no interaction, until they touch each other). Therefore, a
random walker molecule would keep on colliding with other molecules and continue to get displaced
Diffusion coefficient for gases is given by: which is dependent on T, pt and molecular weight.

Diffusion in liquids: In liquids the interaction between molecules is very strong, and the average number
of collisions is very large (compared to mean free path.). Diffusion in liquids is based on Stokes Einstein
relation. Stokes Einstein relation is valid when the diffusing molecule (for example, solute or colloidal
particle) size is much larger than the surrounding molecules (solvent).The shape of the diffusing
molecule is also assumed to be spherical.
Many molecules, however, are non- spherical. Stokes Einstein relation can be modified for nonspherical shapes. Therefore, Stokes Einstein relation is used as a basis for situations where molecules
are comparable to surrounding molecules as well as when molecules are non-spherical. The diffusivity
given by this relation is D= KT/6
.where K is Boltzmanns constant, T is temperature, is viscosity
and a is radius of the sphere.

Diffusion in solids: The random walk model is useful to think about diffusion in solids also. The adjoining
figure shows possible paths or jumps by a diffusing atom: There are 12 possibilities of steps. When large
number of steps are taken, it can be shown that the mean square distance traveled is nl2, as discussed
earlier. Based on this, the diffusivity for solids (With vacancy diffusion) can be shown to be D= ao2N vW
Where a0 is lattice length, Nv is the mole fraction of vacancy sites and w is jump frequency of atoms.

The random walk process depends on the thermal energy available, is an example of activated process.
Therefore, diffusivity as a function of temperature is given by,

Important dimensionless numbers: Differential statement of linear momentum balance and species
balance:

Based on the theory discussed above, idealized problems related to mass transfer are solved. The
objective will be to set-up the governing equation (differential equations), specify the boundary
conditions and solve for concentration profiles. For each of these problems, a suitable mass transfer
coefficient can be defined.
Steps used in each problem:
1. Specify the problem
2. Simplify governing equation
3. Specify initial and boundary conditions
4. Solve the equation/s
5. examine/understand properties of the solution
6. Relate to mass transfer coefficient
7. Discuss limitations / further extensions

Some of the problems solved are listed below:

Diffusion from sphere
Unsteady diffusion in planar geometries: semi-infinite slab, slab of finite dimensions.
Diffusion in a falling film
Boundary layer over a at surface
Diffusion with turbulence
Diffusion with reaction
Diffusion in a catalyst pellet
Turbulant flow: the velocity at a given point fluctuates even if average velocity with respect to time, at
that point, is constant. Therefore, we can write velocity component in x - direction at some point as:

Where the average velocity is defined:

Where T is the time window over which averaging is done. This is because, over this time window the
fluctuations are random and therefore, their averages are zero. This window is large enough to average
out the fluctuations. The averaging is used in the following way:
Define average variables, for which fluctuations exist
Use the definitions of averaging to obtain the averaged versions of the governing equations
Attempt to solve for averaged variables.
Analyze the variations of averaged variables
Boundary conditions for mass transfer problems: For the solution of idealized problems, we mainly
used concentration boundary conditions. In many realistic applications, different types of boundary
conditions are valid
Time dependent concentration: When component diffuse in/out of domain, the concentration
in the surrounding medium changes.
Flux boundary condition
Composite media (1 and 2) boundary condition

Constant flux at the interface: due to reaction, for example rate of production of a species at the
electrode based on the current being passed
Impermeable surface: flux at these surfaces is zero.

Moving boundary: Interface changing due to flow or phase change. For example, above a certain
concentration diffusivity changes. This will lead to a moving front and boundary condition at
that moving front.

Simultaneous heat and mass transfer: Most mass transfer operations involve simultaneous heat
and mass transfer, such as evaporation, adsorption etc. In these cases, boundary conditions are
linked with heat of evaporation etc.

Film theory of mass transfer: It is the simplest theory. The features of film theory are shown in Fig and
they are:
It is assumed that next to the interface, a thin film exists. The thickness of this fictitious film is ZF .
Mass transfer resistance is confined to this film.
It ensures that concentration is uniform out- side the film. Molecular diffusion takes place within the
thin film. Concentration varies linearly within the film.
For better mass transfer, the film should be as thin as possible.

The mass transfer and heat transfer coefficients are still called film coefficients.
Solution for component balance for steady one-dimensional diffusion across a stationary thin film is:

Therefore, mass transfer coefficient and Sherwood number according to film theory are:

Penetration theory:
The features of penetration theory are shown in Fig. 6.3 and they are:
Complicated contacting of two phases can be simplified based on Concepts of fluid packets (eddies).
Liquid packets moving around a bubble: engaging and disengaging. Liquid eddies rising to the
interface (due to turbulence) moving along the interface for some time and moving to the bulk. There is

a finite time over which mass transfer from one phase to another takes place. This contact time is same
for all fluid packets.
Initial concentration in the eddy is CAO and the interfacial concentration is CAI.
During each contacting (exposure of eddy to the interface) A penetrates to the small distances due to
relatively short times of contact.
Penetration theory

Solution for component balance for unsteady one-dimensional diffusion is:

Mass transfer coefficient, based on the solution, is:

Combined film penetration: Penetration theory assumes that the fluid eddies to be effectively infinite.
However, combined film-penetration theory takes concentration to be CAO at finite distance away from
the interface. Therefore, cA0 at Z=Zb. Based on this theory, the mass transfer coefficient was evaluated
as:

Where s is surface renewal rate. When penetration is rapid (large DAB), the equation reduces to film
model, while for lower DAB, this model reduces to penetration model.
There are other modified theories namely surface renewal theories, surface stretch theory.
Maxwell-Stefan diffusion relations:
Based on mechanical theories, the linear momentum on a species can be written as,

The effect of component velocity due to diffusion is based on,

velocity difference of two components
amount of two components
friction coefficients AAi
summing over all binary pairs

Diffusion terms can also be argued based on collisions and kinetic theory. Let us say that particles of
species and 1 and 2 are colliding and exchanging momentum. Velocities of particles before and after
collision are u1, u2 and u1, u 2, respectively. It can be shown that, on average, the momentum
transferred by particle 1 to particle 2 will be:

This implies that the momentum exchange is proportional to difference of component velocities. The
number of such collisions will be proportional to the amount of 1 and 2. So, the momentum exchange
will be proportional to concentrations / mole fractions of 1 and 2 .
The momentum exchange (between molecules 1 and 2) in an elemental volume element of thickness z
is equal to the momentum exchange between molecules and the wall of the elemental volume (partial
pressure of molecules 1 and 2). Therefore, we can write that:

In the above equation, a friction coefficient or inverse of the friction coefficient (diffusivity) can be
introduced:

These equations can also be written in the form of gradients of mole fractions:

From the explanation based on kinetic theory, we can argue that momentum exchanges by multiple
components can be summed together to find the overall momentum exchange on a particular
component. Therefore, the composition gradient in a multi-component mixture can be written as,

Where DAi = DiA. The above equation can be written in the form of molar flux of components as,

Alternately, this equation can be written in terms of diffusion fluxes,

These Maxwell-Stefan relations are valid for multi-component mixtures of ideal gases. For non-ideal
mixtures of gases and liquids, these relations are written in terms of gradients of chemical potential:

In case of ideal gas mixtures, A = RTlnxA. For non-ideal mixtures, the chemical potential can be written
in terms of activity coefficient or fugacity coefficient. It can be shown that,

Binary systems: For binary systems equation can be simplified to

This is same as Ficks law and therefore, for an ideal gas binary system Fick diffusivity and Maxwell
Stefan diffusivity are the same.
Similarly:

If we use Margules equation to describe the activity coefficient in the binary mixture,

Therefore, we obtain the thermodynamic factor required for the Maxwell Stefan relation:

The Ficks diffusivity will can be written in terms of Maxwell Stefan diffusivity,

Ternary systems: It can be shown that composition gradients are related to diffusion fluxes through a
matrix of coefficients. These matrix coefficients are functions of Maxwell-Stefan diffusivities and
composition. Interpretation of the matrix coefficients in terms of Ficks diffusivity leads to the
observation that this diffusivity varies with composition, even for ideal gas mixture.

Equilibrium staged operations

THE MAIN TOPICS OF INTEREST ARE:
GAS ABSORPTION
DISTILLATION
EXTRACTION
LEACHING
GAS ADSORPTION.

The driving force for any mass transfer operation depends on the distance between the equilibrium line
and the operating line. When the two lines touch there is no driving force and the mass transfer stops.
Gas-liquid absorption: solute is absorbed by a solvent (liquid) from gas stream. Liquid solvent should be
rich in solute after absorption.
The number of stages required depends on the solvent flow rate. Higher flow rate requires less number
of stages.
Stripping: gas strips the solute from the liquid. It is opposite of absorption. For same components, same
T and P, same gas, same liquid and same solute, both the stripping and absorption will have the same
equilibrium relationship.
Reference page numbers: treybal (page 275 to page 333).
Liquid-liquid extraction: countercurrent, crosscurrent or concurrent type of contactors can be used. In
case of single stage operation the use of any type of contactors gives the same output. Compositions but
in case of multistage contactors the countercurrent operation gives maximum efficiency.
In case of concurrent operation addition of another stage is meaningless in ideal situations.
Multi stage countercurrent contactors result in greater degree of separation at each stage. For a given
solvent flow rate the number of stages required for the separation is lowest in countercurrent mode of
operation.
Cremsers equation (please refer treybal for the equation) is used for various calculations in the
countercurrent mode of operation.
Absorption factor: Rs / mEs.
Reference page numbers: treybal (page 117 to page 134).
Flash Vaporisation: the liquid feed is flash. Vapor is formed at the expense of liquid.
= (V/F) (fraction of feed vaporized)
Zi = (1- ) xi + yi
yi = Ki xi ( equilibrium relationship)
i=1c zi/(1+ (Ki-1)) = 1
The above summation can be solved using Newton raphsons method
Distillation: This type of separation is used when the different components to be separated have
different volatilities.
Relative volatility ( AB) = (yA /xA)/(yB /xB).
should either be greater than 1 or less than 1 for the components to be separated using distillation. If
is one then distillation cannot be applied for their separation.
Distillation column: It consists of enrichment section and stripping section.
The top section of the column is enrichment section and the bottom section is called stripping section.
Enrichment section: condensation of the heavier component takes place and hence results in the
enrichment of the lighter component.
Stripping section: evaporation of the lighter component takes place.
Even when two liquids of same latent heat flow in opposite direction, mass transfer still takes place but
the flow rate of the liquid stream and the vapor stream remains unchanged.
MC CABE AND THILE METHOD:
Assumptions:

The column is thermally insulated i.e. no heat is lost to the surroundings or gained from the
surroundings.
Constant molar flow rates.
Same latent heat of vaporization for the different components to be separated.
Reflux ratio (R) = Lo/D
Where Lo is the reflux and D is the distillate.
Operating line for enriching section:
yn+1 = (R/R+1)xn + (xD/R+1).
Operating line for stripping section:
ym+1 =( L/G)xm ( W/G)xB .
where L = L + q*F
G = G + (1-q)*F
q line equation:
y=(q/q-1)x - (zf /q-1).
q = 1 for saturated liquid feed.
q < 0 for superheated vapor feed.
q >1 for sub cooled liquid feed.
0 <q<1 for a mixture of saturated vapor and saturated liquid feed.
q=0 for a saturated vapor feed.
Equilibrium stage: the two exiting streams are in equilibrium.
CONDENSERS:
Partial condensers: they also behave as an additional stage and hence separation occurs. Flash
condensation takes place in the condenser.
2. Total condensers: no separation takes place in this type of condenser only heat exchange takes
place.
REBOILERS:
Partial reboilers: they also behave as an additional stage and hence separation occurs. Flash
evaporation takes place in this type of reboiler.

Total reboilers: no separation takes place in this type of reboiler.

Total reflux condition: distillate (D) is zero and bottoms flow rate is (B) is zero. The slopes of both
enrichment section and stripping section become equal to 1. This condition gives the minimum number
of trays.
Fenskes equation: can be used only in total reflux condition.
(xD /1-xD) = (avg) np+1(xB /1-xB).
Where np+1 are the total number of stages.
Reference page numbers: treybal (page 367 to page 374 , page 382 to page 388 and page 402 to page
426).
BATCH DISTILLATION: used for small scale operation, used for fine chemicals of high purity, frequent
changes in the feed to be handled and product specifications.
Rayleighs equation:

Assumptions:
Vapor is always in equilibrium the liquid.
Vapor leaves the batch still and condenses outside only.
vapor composition changes as the liquid composition changes.
Vapor doesnt entrain any liquid.
Equation:
FB (dL/L) = xFxB ( dx/y*- x).
If we need constant purity of the distillate then either the temperature should be increased or reflux
should be increased.
Reference page numbers: treybal ( pg 367 pg 371)
AZEOTROPIC DISTILLATION: the relative volatility of the components is very close to one in this case.
Entrainer is used in this type of distillation.
Reference page numbers: treybal ( page 352 to page 353 and page 455 to page 460).
EXTRACTIVE DISTILLATION: used for separation when is nearly equal to one. When A and C (solute)
are difficult to separate a solvent B is added. The solvent selection is based on the hydrogen bonding
criterion and the polarity of the solvent.
Reference page numbers: treybal (page 477 to page 499)
DUAL SOLVENT EXTRACTION: the feed is a mixture of two solutes (say B and C) and let A and D be two
immiscible solvents. The feed is introduced onto the feed tray. The two immiscible solvents flow in
counter current direction. Solvent A dissolves B and solvent D dissolves C. There are two operating lines
and an equilibrium relation in this type of extraction.
Reference page numbers: treybal (page 514 to page 518).
GAS ADSORPTION:
Adsorbent: solid.
Adsorbate: substance that gets adsorbed.
When pressure equals vapor pressure, liquid condenses and it is not called adsorption.
Desired properties of adsorbents:
It should have less pressure drop.
It should have high surface area.
It should be free flowing.
Physisorption: depends on vanderwaals forces, multi layer and reversible.
Chemisorption: it is highly selective in nature and it is irreversible
DESORPTION: it is the reverse phenomenon of adsorption. Desorption is assumed to be independent of
pressure.
Adsorption and desorption are in equilibrium always.
= (Kp /Kp+1)
Where is the fraction of sites occupied on the adsorbent.
p is the pressure.
K= ( Ka / Kd ).
For Langmuir adsorption model please refer treybal.

Reference page numbers: treybal (page 565 to page 612