MASS TRANSFER

 MASS TRANSFER OPERATIONS BY TREYBAL

 TRANSPORT PHENOMENA By BIRD
 HEAT & MASS TRANSFER A PRACTICAL APPROACH
BY CENGEL
 TOPICS TO BE COVERED
• Introduction to Mass Transfer
• Modes of Mass Transfer
• Classification of Mass Transfer Operations
• Choice of Separation Method
• Design Principles
• Mass Transfer Theories
• Interphase Mass Transfer / Mass Transfer Coefficient
Approximately first 5 chapters of “Mass Transfer Operations by
Treybal”
 INTRODUCTION TO MASS TRANSFER
• MTO’S, largely the responsibility of the chemical engineer
• However increasingly practitioners of other engineering disciplines are finding them
• Either necessary for their work,
• Humidification and dehumidification
• Pollution Control
• Heat transfer accompanied by mass transfer with or without chemical reactions.
Rocket motor design or Cooling Towers
• Or working in industry parallel to chemical engineers need an understanding of MT
• A number of MTOs’ are concerned with changing the compositions of solutions and
mixtures through physical methods instead of chemical
• Mechanical operations directed toward separating a substance into its component;
• Filtration of a solid from a suspension in a liquid
• Classification of a solid into fractions of different particle size by screening
• Separation of particles of a ground solid according to their density
• If operations involve changes in composition of solutions  known as MTOs’
• Major part of the cost of a process is that for the separations.
• Separation or purification costs depend directly upon the ratio of final to initial
concentration of the separated substances
• Sulfuric acid is a relatively low-priced as sulfur is found naturally in a
relatively pure state
• Pure uranium is expensive because of the very low natural concentration
 CLASSIFICATION OF MTOs’
MTOs’ are characterized by transfer of one substance through another
on molecular scale
DIRECT CONTACT OF TWO IMMISCIBLE PHASES
(Most important of all MTOs’)
 2-phase system of several components at equilibrium (with few
exceptions) the compositions of the phases are different
 Various components are differently distributed between the phases
 In MTOs’ neither of the equilibrium phases// consists of only one
component
 Consequently when the two phases are initially contacted, they will
not be of equilibrium compositions
 The contacted system then attempts to reach equilibrium by a
relatively slow diffusive movement of the constituents, which
transfer in part between the phases in the process.
 Separations are therefore never complete, although, can be brought
as near completion as desired (but not totally) by appropriate
manipulations
 CLASSIFICATION OF MTOs’
MTOs’ are characterized by transfer of one substance through
another on molecular scale
Example:
 Water evaporates from a water surface into an airstream flowing over it
 Liquid water molecules evaporate gets converted into water vapours
 Molecules of water vapor diffuse through those of the air present at the
water surface into the main portion of the airstream, from where they are
carried away.
 The water molecules do not move in bulk due to the pressure difference, as
in pumping a liquid through a pipe
 Hence, the mass transfer is a result of a concentration difference, or
gradient, under which the diffusing substance move from a place of high
concentration to one at low concentration.
 CLASSIFICATION OF MTOs’
• Gas-gas
Completely soluble hence generally not applicable and difficult to seprate requires
special techniques
• Gas-Liquid
Distillation, Gas Absorption, Desorption, Humidification or dehumidification
• Gas-Solid
Sublimation, Adsorption, Drying
• Liquid-Liquid
Liquid-liquid extraction
• Liquid-Solid
Leaching, Crystallization
• Solid-Solid
Very slow diffusion process hence no industrial scale process exists
 CLASSIFICATION OF MTOs’
PHASES SEPARATED BY A MEMBRANE
• Operations used relatively infrequently but rapidly increasing in importance
• Different membranes operate differently depending upon nature of separation
• Membranes prevent
• intermingling of two miscible phases
• ordinary hydrodynamic flow. Substances move through them by diffusion
• They permit a component separation by selectively controlling passage of
the components from one side to the other
• Gas-gas
Gas diffusion or effusion
• Gas-Liquid
Permeation
• Liquid-Liquid
Dialysis, Osmosis
DIRECT CONTACT OF MISCIBLE PHASES
Thermal Diffusion, Centrifuge
 CLASSIFICATION OF MTOs’
DIRECT vs INDIRECT OPERATIONS
Direct operations produce the two phases from a single-phase solution by
addition or removal of heat.
• Fractional distillation, fractional crystallization, Fractional Extraction
Characteristics
• Products are obtained directly, free of added substance
Indirect operations involve addition of a foreign substance
• Gas absorption and stripping, adsorption, drying, leaching, liquid
extraction, and certain types of fractional crystallization.
Characteristics
• Removed substance is obtained as a solution,
o which must be separated, either to obtain the pure substance or
for reuse, hence expensive
• Separation of added substance and product can’t be complete
o leading to difficulty in meeting product specifications
• Addition of a foreign substance may add to the problems
o of building corrosion-resistant equipment, hence increased cost
 CLASSIFICATION OF MTOs’
DIRECT vs INDIRECT OPERATIONS
• Obvious, indirect methods are used only because they are
• in the net, less costly than the direct methods if there is a choice and
frequently there is no choice.
• When the separated substance need not be obtained pure,
• many of the mentioned disadvantages disappear.
• For example, in ordinary drying, the water vapor-air mixture is
discarded since neither constituent need be recovered.
• In the production of HCl by washing a hydrogen chloride-containing gas
with water, the acid-water solution is sold directly without separation
 CLASSIFICATION OF MTOs’
CHOICE OF SEPARATION METHOD
• To choose a particular separation method is a problem faced by engineers
• Choice is usually limited by the peculiar physical characteristics of the
materials to be handled
• Unless fundamentals of various operations have been clearly understood,
no basis for such a decision is available
• Generally the choice can be made between one of the mass-transfer
operation already discussed and a purely mechanical separation method
• Extraction of vegetable oil from seeds can be mechanically done or by
solvent extraction
• Sometimes both mechanical and mass-transfer operations are used,
• especially where the former are incomplete, as in above example where
mechanical extraction is followed by solvent extraction
 CLASSIFICATION OF MTOs’
CHOICE OF SEPARATION METHOD
• Sometimes choice has to made between a pure physical mass-transfer
operation and a chemical reaction or a combination of both.
• Water can be removed from an ethanol-water solution either by causing it to
react with unslaked lime or by special methods of distillation
• Hydrogen sulfide can be separated from other gases either by absorption in a
liquid solvent with or without simultaneous chemical reaction or by
chemical reaction with ferric oxide.
• Chemical methods ordinarily destroy the substance removed, while mass
transfer methods usually permit its eventual recovery in unaltered form
usually without great difficulty
 CLASSIFICATION OF MTOs’
CHOICE OF SEPARATION METHOD
Choices to be made among the the mass-transfer operations
A gaseous mixture of oxygen and nitrogen may be separated by
• preferential adsorption of the oxygen on activated carbon
• distillation
• gaseous effusion
A liquid solution of acetic acid may be separated by
• distillation
• liquid extraction with a suitable solvent
• adsorption with a suitable adsorbent
Principal basis for choice in any case is cost: that method which costs
the least is usually the one to be used
Occasionally other factors also influence the decision, however.
• Simplest operation, may be costly, is desired as it will be trouble-free
• Sometimes a method is discarded as adequate knowledge of design
methods is not available
• Unavailability of data for design, so that results cannot be guaranteed
Favorable previous experience with one method may be given strong
consideration
 CLASSIFICATION OF MTOs’
DESIGN PRINCIPLES
Design of any plant involving diffusional operations require four major factors:
1. Number of equilibrium stages or their equivalent
2. Time of phase contact required
3. Permissible rate of flow
4. Energy requirements
Number of equilibrium stages or their equivalent
Definition of a Stage (Equilibrium Stage)
If two insoluble phases are allowed to contact so that the various diffusing
substances can distribute themselves between the phases, and if the phases
are then mechanically separated, the entire operation and the equipment
required to carry it out are said to constitute one stage,
To determine the number of equilibrium stages required in a cascade to bring
about a specified degree of separation, or the equivalent quantity for a
continuous-contact device one requires the following two,
1. The equilibrium characteristics of the system
2. Material-balance calculations
3. The Energy Balance also in some cases
 CLASSIFICATION OF MTOs’
DESIGN PRINCIPLES
Time Requirement
Time of contact is intimately connected with stage efficiency
For continuous-contact equipment the time leads ultimately to the volume or
length of the required device
Factors which help establish the time are several
• Material balances permit calculation of the relative quantities required of
the various phases
• Equilibrium characteristics of the system establish the ultimate
concentrations possible
• Rate of transfer of material between phases depends upon
• Departure from equilibrium which is maintained
• Physical properties of the phases
• Flow regime within the equipment

• Important to remember that, for a given degree of intimacy of contact of the

phases, the time of contact required is independent of the total quantity of
the phases to be processed.
 CLASSIFICATION OF MTOs’
DESIGN PRINCIPLES
Permissible Flow Rate
• This factor enters into consideration in case of semi-batch and steady-state
operations
• Required for the determination of the cross-sectional area of the equipment
• Considerations of fluid dynamics establish the permissible flow rate
• Material balances determine the absolute quantity of each of the streams
required
Energy Requirements
• Heat and mechanical energies are required to carry out the diffusional
operations
• Heat is necessary for the production of any temperature changes, for the
creation of new phases (such as vaporization of a liquid), and for
overcoming heat-of-solution effects
• Mechanical energy is required for fluid and solid transport, for dispersing
liquids and gases, and for operating moving parts of machinery
 MODES OF MASS TRANSFER
MASS TRANSFER MODES
DIFFUSION CONVECTION

MOLECULAR KNUDSEN, ONLY IN GASES

Diffusion, when the scale length of a system
is comparable to or smaller than the mean
free path of the particles involved.
Long pore with a narrow diameter (2–50
nm) as molecules frequently collide with the
pore wall
A process involving the motion of adatoms, molecules, and atomic clusters
(adparticles) at solid material surfaces.
Can be thought of in terms of particles jumping between adjacent adsorption
sites on a surface.
A thermally promoted process with rates increasing with increasing
temperature
IN GENERAL MASS TRANSFER BY DIFFUSION IS MORE COMPLICATED THAN
VISCOUS FLOW OR HEAT CONDUCTION BECAUSE WE HAVE TO DEAL WITH
MIXTURES (MORE THAN ONE COMPONENT)
 BASIC DEFINITIONS -1
mass of j
MASS CONCENTRATION j 
volume of solution

j moles of j
MOLAR CONCENTRATION cj  
Mj volume of solution

j  mass of j
j   n j 

 k
MASS FRACTION total mass

k 1

cj cj mole of j
xj   n

c
MOLE FRACTION c total moles
k
k 1

The word “solution” means one phase

gaseous, liquid or solid mixtures
 BASIC DEFINITIONS, contd. -2
VELOCITIES AND AVERAGE VELOCITIES

Why we need the velocities and average velocities

• Various species move at different velocities
• However, the bulk velocity of the solution remains constant

Let vj be the velocity of the species j relative to the stationary coordinate

‘velocity of species j,” does not mean

Local mass average velocity
the velocity of an individual molecule
of MIXTURE is defined as
of species j. Rather, the average of all
the velocities of molecules of species a
within a small volume

n n

 v k k  v k k n
k n
v k 1
 k 1
  v k   ωk v k
n
 k 1 

k 1
k
k 1
 BASIC DEFINITIONS, contd. -3
This mass average
 total mass   distance  velocity of mixture
Note that v     is the local velocity
 volume   time 
one would measure
by a pitot tube
It is the local mass rate through a unit cross section
placed perpendicular to the velocity v

THE LOCAL MOLAR AVERAGE VELOCITY IS DEFINED AS

n n

The local molar c v k k c v k k n

ck n
average velocity of v 
* k 1
n
 k 1
  v k   xk v k
c
mixture is defined as: c k 1 c k 1
k
k 1

 total moles   distance 

Note that cv  
*
 
 volume   time 

It is the local molar rate through a unit cross

section placed perpendicular to the velocity v*
 BASIC DEFINITIONS, contd. -5
MASS AND MOLAR FLUXES RELATIVE TO STATIONARY COORDINATES

Total  mass of species j   distance 

Mass flux n j  ρ jv j    
of species j  volume   time 

which is the total mass

of species j transferred
per unit time and per
unit area normal to the
velocity vj

Total  moles of species j   distance 

Molar flux N j  c jv j    
of species j  volume   time 

which is the total moles

of species j transferred
per unit time and per
unit area normal to the
velocity vj
 BASIC DEFINITIONS, contd. -4
DIFFUSION VELOCITIES

In flow systems, very often that we are interested in the velocity of species j w.r.t, v or v*

with respect to the stationary coordinates. Here, we talk of

rather than
the diffusion velocities, and there are two diffusion velocities

 diffusion velocities of   diffusion velocities of 

vj - v    vj - v  
*
*
 species j with respect to v   species j with respect to v 
Diffusion velocities
Bulk velocity
There are two diffusion
Mixture velocities. In applications
where we deal with molar
flow, the diffusion velocities
Species -1 with respect to v* will be used

Diffusion Convection
 BASIC DEFINITIONS, contd. -6
DIFFUSIVE MASS AND MOLAR FLUXES

Mass fluxes relative to the Molar fluxes relative to the

local mass average velocity local molar average velocity

jj  ρ j  v j  v  J j  c j  v j  v* 

PROPERTIES OF DIFFUSIVE FLUXES

n n

j
k 1
k   k  vk  v 
k 1
n n n

j k 0
Can
n
  k v k  v k
n
 v k k  v k k
k 1 k 1 k 1 v k 1
 k 1
n

 k
You n
Prove    k v k  v  0 k 1
this k 1
n n
k n

J 0
n
  v k   k v k
k 1
k
 v k k k 1  k 1
since v  k 1

Go To Slide 5

Similarly for the molar based
 BASIC DEFINITIONS, contd. -6
n
Interpretation of J
k 1
k 0

This equation means that within the movement of the bulk

fluid mixture, the sum of all the diffusive fluxes must be zero
so that the pressure is maintained constant.

Hence, for a binary mixture

J1  J 2

TWO SPECIES MOVE IN THE OPPOSITE DIRECTION

(RELATIVE TO THE MOVEMENT OF THE MIXTURE)

THIS GIVES RISE TO THE CONCEPT OF

EQUIMOLAR COUNTER DIFFUSION
 BASIC DEFINITIONS, contd. -6
DIFFUSIVE MASS FLUXES VERSUS TOTAL AND CONVECTIVE MASS FLUXES

jk   k  v k  v 
Can
n n
jk  n k  k  n j You
 v j j
Prove j 1
j1
 k vk  k
this 

k n
  k v k    jv j
 j 1

This equation simply states that the diffusive n

mass flux of species J is equal to the total jk  n k  k  n j
mass flux minus its contribution in the total j1
flux (convection only)

n
DIFFUSIVE MOLAR FLUXES J k  N k  xk  N j
VERSUS MOLAR FLUXES j1
 BASIC DEFINITIONS, SUMMARY
Total Flux
• Amount of a quantity passing through a unit surface area per unit time

Convective Flux
• Amount of a quantity passing through a unit surface area per unit time that
is carried by some reference velocity
Diffusive Flux
• Amount of a quantity passing through a unit surface area per unit time due
to diffusion
• The difference between the Total Flux and the Convective Flux
• Cannot be defined independently of the total & convective fluxes

Total Fluxes written in terms of component’s velocity & specific density

Mass Flux of component i Total Mass Flux

n n
n i  ρi vi  i ρvi n   ni   i vi  v
i 1 i 1

 = mixture mass density

 BASIC DEFINITIONS, SUMMARY
• Total flux is partitioned into a convective and diffusive flux
• Convective flux is defined in terms of an average velocity
• Diffusive flux is defined as the difference between the total
and convective fluxes.
It is only defined once we have chosen a convective flux!

Mass diffusive flux of Convective flux of

Total mass flux
component i relative to a component i due to a
of component i
mass-averaged velocity. mass-averaged velocity

jk  k v k - k v = n k  k v

(Diffusion flux) = (Total Flux) - (convective flux)

 Fick’s law of diffusion for binary mixtures
Experience suggests the following.
1. A molar flux always occur with in a fluid mixture if there exists a
concentration difference. This molar flux J is directly proportional to
1. Concentration difference
and is inversely proportional to
1. Distance between the regions where conc. difference occurs

Mathematical Interpretation of Experience

c/z is the concentration gradient
c c
J  J D c dc
z z 
z dz

The basic equation for Fick’s law for dx1

an isobaric and isothermal system is:
J1  cD12
dz

Similarly, we can write an equation dx 2

J 2  cD21
for the second species: dz
 Diffusion coefficient
 m2 
Units D12   
 sec 

State Order of magnitude (cm2/sec)

Gas 0.1 - 1
Order of magnitude
Liquid 110-7 - 110-5

Solid 110-12 - 110-7

Temperature and pressure dependence

For gases at low density, D increases with T and decreases with pressure
For liquids and solids, D increases with temperature.
Shell Balance Mass Transfer of Binary Mixtures
Procedures for binary mixtures
Similar to those we learnt earlier for momentum and energy transfers.
Steps 1 to 4: Draw a physical diagram and a thin shell with surfaces
perpendicular to transport directions.
Step 5: Set up mass balance equation for the specie of interest for the
thin shell w.r.t stationary coordinates
 Rate of   Rate of   Rate of mass 
     Accumulation
 Mass In   Mass Out   Production 
Taking the shell as thin as possible will yield a first order differential equation
in terms of molar flux.
Step 6: Apply the Fick’s law
dx
Flux due to diffusion N Az = - c DAB A  x A  N Az  N Bz  Flux due to total
dz molar bulk flow

or in three dimensional coordinates

Depending on the physical system, NB must
NA = - c DABx A  x A  NA  NB  be determined based on the physical ground.
 Shell Balance Mass Transfer of Binary Mixtures -2
Step 7: Impose physical constraints
Step 8: Solve for concentration distribution
Step 9: Solve for desired quantity, such as average concentration,
molar fluxes.

BOUNDARY CONDITIONS

Generally, there are five boundary conditions:

B.C. of the 1st kind: Concentration is specified at the boundary
B.C. of the 2nd kind: Molar flux is specified at the boundary
B.C. of the 3rd kind: Molar flux into the medium is the same as the flux
through a stagnant film surrounding the medium
B.C. of the 4th kind: Concentrations and fluxes are continuous across
the interface of two adjoining media.
B.C. of the 5th kind: Molar flux is equal to the surface reaction
 Shell Balance Mass Transfer of Binary Mixtures -3
How to handle NB in the shell balance equation

A non-reacting system A reacting system

NB determined on
some available A homogeneous A heterogeneous
physical realities reacting system reacting system

NB is defined as NB is defined as
a source term a surface BC

Be careful about
One needs the info
the units of k
of reaction kinetics
N Az surface
 kn cAn
surface
RA  kn c An
 Example: Diffusion in a Stefan tube

Physical system
1. Liquid 1 in the tube
2. Gas 2 flowing across the mouth of tube
z2 3. Gas 2 is non-soluble in liquid 1

z1
Step 5: Shell mass balance

 Rate of   Rate of   Rate of mass   Rate of mass 

=      =  
 mass in   mass out   Production   accumulation 

SN1 z  SN1 z z  0  0

 Example: Diffusion in a Stefan tube -2
Taking the shell as thin as possible:
dN1 which simply states that the molar
 0 flux is constant along the tube
dz

Step 6: Apply the Fick’s law

dx1
 x1  N1  N 2 
is equal to zero as the species 2 is non-soluble in
N1  - c D12
dz liquid 1. This is called the bootstrap condition

Thus, we solve for N1 in terms of the concentration gradient

- c D12 dx1
N1  Substitute this into the
1- x1  dz mass balance equation:

d  c D12 dx1  For constant total pressure and d  1 dx1 

   0    0
dz  1- x1  dz  constant diffusion coefficient dz  1- x1  dz 

a second-order differential equation in terms of mole fraction.

 Example: Diffusion in a Stefan tube -3
Step 7: Physical constraint; The two boundary conditions are:
Vapor pressure at gas-liquid
0
p surface else partial pressure
at z  z1 ; x1  x1,0 
1

P Total pressure
z  z2 ; x1  x1, L

 c D12 dx1   1 
Step 8: Concentration distribution    K1 c D12 ln    K1 z  K 2
 1- x1  dz   1- x1 

Here, we have two constants K1 and K2 so apply the two boundary conditions:

 1   1 
at z  z2   K1 z2  K 2 at z  z1 c D12 ln   K1 z1  K 2
c D12 ln 
 1- x  1- x 
 1, L   1,0 

Solving for K1 and K2, we get

c D12  1- x1,0   1  c D12 z1  1- x1,0 

K1  ln    c D12 ln    ln 
 1- x 
K2
z2 - z1  1- x1, L   1- x
 1, L  z 2 - z1  1, L 
 Example: Diffusion in a Stefan tube -4
Thus, the concentration profile is:

 z - z1   z2 - z1 
 1- x1   1- x1, L 
    
 1- x1,0   1- x1,0 

Step 9: Molar flux

The quantity of interest is the molar flux from the liquid surface (evaporation rate):
- c D12 dx1
N1 
1- x1  dz
Where should we evaluate the above derivative to obtain the evaporation rate? At
the liquid surface?
OR IT CAN BE dN
- c D12 dx1
N1  CALCULATED AT  1 0
1- x1  dz z  z1 SOME OTHER z dz

c D12  1- x1, L  Finally The it can be evaluated anywhere as

N1  ln  
z2 - z1  1- x1,0 
Molar Flux the N1 is constant along the tube.
 Example: Diffusion in a Stefan tube -5
If the gas 2 is sweeping past the mouth fast enough, the concentration of the
species 1 at the mouth will be effectively zero; hence the evaporation rate is

N1 
c D12  1 
ln  Written in terms
N1 
P RT  D12  1 
 ln  
z2 - z1  1- x1,0  of pressure z2 - z1  1- p1
o
P 

N1 +N 2 
P RT  D12  1 
What about the total molar flux ln  o 0
z2 - z1  1- p1 P 

Go to slide 17
dx2
What about the molar N 2  - c D12  x2  N1  N 2 
dz
flux of species 2
dx2   P RT  D12  1  
N 2  - c D12  x2  ln  o   N2   0
dz  z2 - z1  1- p1 P  

diffusive flux convective flux

0, the bootstrap condition
down the tube up the tube
 Steady State Diffusion in Fluids at Rest OR in Laminar Flow
Starting with the situation in the Stefan’s Tube Shell Balance leads to

dx
N1  - c D12 1  x1  N1  N 2 
0
c1 p1 n P
dz x1   c 
c P V RT
dc1 c1   N1  N1  N 2   P  p1,2
N1  - D12   N1  N 2  
o
N1 PD12
dz c N1 = ln  
N1  N 2 RT  z2 - z1    N1  N1  N 2   P  p1,1 
 o 

c1,2
dc1
z
1 2
 N1c  c1  N1  N 2 
 
cD12 z1
dz
c1,1
N1 PD12   N1  N1  N 2    x1,2 
N1 = ln  
N1  N 2 RT  z2 - z1    N1  N1  N 2    x1,1 

N1 cD12  N1  N1  N 2   c1,2 c 
N1 = ln  
N1  N 2 z2 - z1  N1  N1  N 2   c1,1 c 

If we assume that ideal gas law is valid

 Example: Diffusion in a Stefan tube -6
Drop in liquid level

Due to evaporation, the liquid level will drop, and to determine this drop in level
versus time, we have to do the mass balance around the liquid.

Rate of change in the volume of liquid in tube = Rate of evaporation of liquid

d  Sz1 L   P RT  D12 ln  1 
 Area  Mol wt  molar flux  -S M L  o 
dt z2 - z1  1- p1 P 

With the initial conditions at t = 0 z = z10, integrate to get

 M L  P RT  D12  1 
 z2 - z1  t     z2 - z10 
2
 2
2
ln   t
 L o
 1- p1 P  

z2 2   z2 - z10 
2

t* 
The time it takes to empty the tube is:  M L  P RT  D12  1  
2 ln  
  L  1- p1
o
P 
Solved Example
Answer:
t* = 651 days

Reasons for this extremely long time required

to empty the tube:
1. low vapor pressure
2. very long diffusion path in the tube
3. very low diffusion coefficient

Conclusion:
1. Diffusion is a very slow process. It is
always advisable to speed up this
process.
2. One way of doing is to reduce the
diffusion path length, achievable in
practice by mixing.
3. Other way is to increase the “D”
 Solved Example -2
What happens if we ignore the convection term Go to slide 17

Then the evaporation rate w/o P RT  D12  p10 P 

N10 =
convection term z2 - z1

Then the evaporation rate N1 

P RT  D12  1 
ln  o 
with convection term z2 - z1  1- p1 P 

Compare the two relations in context with the previous example

Time to empty the tube with Time to empty the tube without
convection term = 651 days convection term = 669 days
 Solved Example -3
To show how much error when the convective
term is neglected, we use the example of benzene
evaporation at 6 and 60 0C

P RT  D12 
ln 
1   1 
o  ln  o 
N1

z2 - z1  1- p1 P    1- p1 P 
N10  P RT  D12  p10 P   p10 P 
z2 - z1

Data
p10= 37 at 6 0C, 395 mmHg at 60 0C.

T oC N1 / For low temperature, the convective

N1 o flux can be ignored but for high
temperature it can not be ignored as
6 1.025
error is 41%.
60 1.41
 DISSOLUTION OF A SPHERE
dr
Sparingly soluble sphere in a
r surrounding fluid of infinite extent.
The object (species 1) dissolves in
surrounding fluid 2 with the solubility of C10

2R The mass balance equation around the thin shell at r

and having a thickness of dr is:

 4 r N    4 r N 
2
1
r
2
1
r r
0 0

Divide the equation by 4πΔr, and take the limit of the result when
Δr approaches zero, we get

 r N    4 r N 
2 2

lim d 2
 
1 1
r 0
r r r
 r N1  0
r dr
 DISSOLUTION OF A SPHERE contd.
Applying the Fick’s Law
dx1
N1  cD12  x1  N1  N 2 
dr
can be taken as zero as the
species 1 (object) is only
sparingly soluble in liquid 2

Thus, the mass balance equation will become:

d  2 dx1 
 r cD12 0
dr  dr 

Boundary Conditions:
1. r=R (surface of object); C1 = C10
2. r → ∞; C1 = 0
 DISSOLUTION OF A SPHERE contd.
R
Concentration distribution C1  CIO
r
D12CIO
Dissolution rate N1 r  R 
R
To increase the dissolution rate:
1. smaller object If we define the mass transfer
2. larger solubility coefficient as:
3. larger diffusivity
N1 r R  km  CIO  0

Matching this with the km  2 R 

solution obtained from first 2
D12
principles, we get:
this is known as the
Schmidt number,
which is equal to 2 for
stagnant environment
Diffusion with heterogeneous reaction-1
The specie A as 1
The specie An as 2

According to the surface chemical

reaction, we must have:
N1 = - n N2

This is the bootstrap condition,

needed in addition to the Fick’s
law equation.

The bootstrap condition in the last

example of the Stefan tube is:
N2 = 0

Step 5: Shell mass balance equation

dN1 which simply states that the molar

 0 flux is constant along the tube
dz
 Diffusion with heterogeneous reaction-2
dx1
Step 6: Fick’s law; The Fick’s law equation is: N1  - c D12  x1  N1  N 2 
dz

1
Bootstrap relation for N2 N2  - N1
n
solving for N1 in terms of the concentration gradient gives:
c D12 dx1
N1  
  n  1  dz
1  x1 
 n 
dN1
Substitute this Fick’s law into the mass balance equation  0
dz
 
 
d  c D12 dx1 
 0
dz    n  1  dz 
1
 
x1 
n  
 
 Diffusion with heterogeneous reaction-3
Step 7: Physical constraints
The boundary conditions will be at two ends of the stagnant film:
BC1: z  0; x1 z 0  x10
B.C. of 5th kind:Molar flux = surface reaction
L = thickness of the film BC 2 : z  L; N1 z L  kcx1 z L
moles of A reacted
kcx1 z  L 
area of catalyst  time
Reaction BC suggests that for very fast reaction k = 

z  L; x1 z  L  0

   
     n  1
d  c D12 dx1  1
 0 c D12 ln   K1 z  K 2
dz    n  1  dz  1   n  1 x1 
n
1
 
x1 
  n 
 n  
2 unknown constants to get using two BC
 Diffusion with heterogeneous reaction-4
 
 1 
BC1: z  0; x1 z 0  x10 c D12ln    K2
1   n  1x 
 n
10


 
nc D12  1 
BC 2 : z  L; x1 z  L  0 K1   ln 
L  n  1   n  1x 

1
 n
10


1 z L
  n  1    n  1 
Finally the concentration profile of x1 1  x1   1  x10 
 n   n 

This shows how the concentration of species 1

distributes itself in the stagnant film

Finally the concentration profile of x2 = 1 - x1

 Diffusion with heterogeneous reaction-5
How to get the reaction rate which is in fact our BC

The reaction rate at the catalytic surface = the flux of x1 at z = L

c D12 dx1
N1 z  L    kcx1 z  L But in our case this is a constant
  n  1  dz
1  x1 
 n  zL

 
  c D12 dx1
  K1
d  c D12 dx1 
 0   n  1  dz
dz    n  1  dz  1  x1 
1  n 
 
x1 
n  
 

 
c D12  1 
Therefore finally N1 z  L   K1  ln    kcx1 z  L
L
 n  1 1    x 
n  1
n  n
10

 Diffusion with heterogeneous reaction-6
Important Inferences from this analysis
 
c D12  1 
N1 z  L   K1  ln    kcx1 z  L
 n  1   n  1 
L 1 x10
n 
 n 
The mass transfer rate is:
1. independent of the reaction rate (system is diffusion controlled)
2. a function of the diffusivity
3. inversely proportional to the film thickness
4. proportional to the total concentration, c
5. a function of the bulk mole fraction
Case, when the chemical reaction is finite
Same analysis but with revised BC2 z  L; N1 z L  kcx1 z L  kcx1L
   
   c D12
d  c D12 dx1  dx1 
 0    K1
dz    n  1  dz  1   n  1 x dz 
1
 
x1   1

n   n
 
 Diffusion with heterogeneous reaction-7
 
 1   n  1
Integrating once more gives: cD12ln   K1 z  K 2
1   n  1x  n
 n
1


 
 1 
at z  0 cD12 ln    K2
1   n  1x 
Applying the BCs’ gives:  n
1o


at z  L K1  kcx1L
Still x1L is unknown, which can be found by setting z = L in the concentration profile

  n  1 
1  n x1L   n  1 k x1L
concentration profile: ln   z
 1  n  1 x1 
n D 12
 n 
 Diffusion with heterogeneous reaction-8
  n  1  n  1   n  1  k L 
Concentration at z = L: ln 1  x1L 1 x10     x1L
 n n  n  D12 
A non-linear algebraic equation in terms of mole fraction at the catalyst surface, x1L
Now the reaction rate cD12   n  1  n  1 x 
N1 z  L  ln 1  x1L 1  10   kcx1L
at the catalytic surface
L
 n  1  n n 
when k is finite n

Compare with the

c D12   n  1 x 
reaction rate at the N1 z  L   K1  ln 1 1  10   kcx1 z  L
catalytic surface when L
 n  1  n 
k is infinite n

  n  1  n  1 x   kL   n  1 
ln 1  x1L 1  10     x1L   Rewriting
 n n   12 
D  n 
 Diffusion with heterogeneous reaction-9
kL chemical reaction rate
A Dimensionless Group
D12 Diffusion rate

CASE: 1 If this group is very large

CHEMICAL REACTION RATE >> DIFFUSION RATE

Then at catalyst surface x1L = 0

cD12  
n
Then the reaction rate

 n  1 
ln 
1  Same expression
N1 z  L  obtained earlier
at the catalytic surface: L 1   n  1 x10  for k = :
 n 

If this group is less than unity

CASE: 2
DIFFUSION RATE >> CHEMICAL REACTION RATE
Fast Diffusion

catalyst surface x1L= x10 Then the reaction rate at the catalytic surface = N1 = kcx10

For fast diffusion chemical reaction is dominated entirely by chemical kinetics

 Diffusion & homogeneous reaction - 1
Now we deal with diffusion and homogeneous reaction within the medium
Difference between this and the last two examples
Reaction term appears in mass balance equation not in BC
Physical system
1. Gas A dissolves sparingly in liquid B
2. Dissolved A reacted with B, following a
nth order reaction, with expression

moles of A reacted
knC1n 
volume-time

3. Isothermal system
4. Let species A be 1, and species B be 2
 Diffusion & homogeneous reaction - 2
@ 1 atm and 20 oC
Gas mole fraction Solubility, in general, increases
SO2 0.03 linearly with pressure and
Cl2 0.0017 decreases with temperature.
H2S 0.002
CO2 0.00062
C2H4 0.0001
CO 0.000018
Step 5: Shell mass balance for first order reaction

 Rate of   Rate of   Rate of mass   Rate of mass 

=      =  
 mass in   mass out   Production   accumulation 

SN1 z  SN1 z z   S z  kC1  0

Negligible because
A is sparingly
soluble in B
dx1
Step 6:Apply the Fick’s law N1  - c D12  x1  N1  N 2 
dz
 Diffusion & homogeneous reaction - 3
dC1 Substitute this Fick’s law into
Thus N1  - D12
dz the mass balance equation

d 2C1
Typical form of simultaneous diffusion & reaction equation D12 2
 kC1  0
dz
Step 7: Physical constraints
BC-1: At the gas-liquid interface, we have the solubility condition:
at z = 0; C1 = C10 (solubility)
For constant T and P, this solubility is a constant
BC-2: The bottom of the liquid pool
At the bottom, mass can not penetrate, thus:
at z = L; N1 = 0
dC1
Using the Fick’s law at this point (z = L) at z  L; N1 z  L   D12 0
dz zL
 Diffusion & homogeneous reaction - 4
 z kL2 
cosh 1   
C1  L  D12 
Step 8: The concentration distribution 
C10  kL2 
cosh  
 D12 
 

Damkohler number Da (1937) named

after a German chemist (1908-1944)

 z  
cosh 1   Da 
C1   L 

C10 
cosh Da 
 Diffusion & homogeneous reaction - 5
Step 9: Mass transfer
To calculate the mass transfer of A (gas absorption rate) into the
liquid B, we simply apply the Fick’s law and evaluate at the gas-
liquid interface.

dC1
N1 z 0   D12
dz z 0

C10 D12
N1 z 0  Da tanh Da
L

C D kL2 kL2
N1 z 0  10 12 tanh
L D12 D12

This is the gas absorption rate per unit interfacial area

 Diffusion & homogeneous reaction - 6
Let’s have a look at the Damkohler number

 L2 
2 
kL  D12  Diffusion time
Da   
D12 1
k  Reaction time

Two extreme cases:

Case 1:
When Da << 1, the diffusion time is very short compared to the reaction time.

This means that dissolved A will have time to penetrate throughout the
liquid B before reaction could take place. One expects:
C1(z) = C10

we take the limit C10 D12 C10 D12

lim N1  lim Da tanh Da  Da  LkC10
Da 0 z 0 Da 0 L L
of the solution

There is no diffusivity term as the system is kinetically controlled

 Diffusion & homogeneous reaction - 7
Case 2: Da >> 1
In this case, the reaction is so fast, so the penetration of the dissolved A can
not go far into the liquid pool.
The gas absorption rate is
C10 D12 C10 D12
lim N1  lim Da tanh Da  Da  C10 kD12
Da  0 z 0 Da  0 L L

Observation:
1. Rate is proportional to the solubility
2. Rate is proportional to square root of chemical reaction rate
3. Rate is proportional to square root of diffusivity
4. Rate is independent of the depth of the liquid pool (is this expected?).
This case is the diffusion-controlled case.
 What will be the ratio of the true absorption rate to the ideal
absorption rate (no effect of diffusion OR absence of diffusion)
Absence of Diffusion/Ideal Absorption/No effect of Diffusion
Rate of reaction that would result if entire interior surface of solution
were exposed to the external surface conditions of concentration for the
given temperature and pressure
C10 D12
N1 z 0 (actual ) Da tanh Da
tanh Da
  L 
N1 z 0 (no diffusion effect ) C10 D12 Da
Da
L

 = the effectiveness factor

 Equations of change for binary mixtures-1
1. Mass units
We apply the law of conservation of mass to an element of volume ΔxΔyΔz, fixed
in space and through which a mixture (species 1 and 2) is flowing.
Also in this volume, there is a chemical reaction per unit volume:
 g produced 
r1 & r2 = 
 cm  sec 
3

The two mass balance equations for the two species are:

1  2
+   n1   r1 +   n2   r2
where n1 & n2 are
t t mass flux of 1 and 2

Sum the two equations to get the total mass balance

  1  2  But
+   n1  n2    r1  r2
t r1+ r2 = 0 conservation of mass

  n1  n2     1v1  2v2    v Finally following eq. of continuity for the mixture


+  v   0
t
 Equations of change for binary mixtures-3
1. Mole units
We have obtained necessary equations written in mass units. Now let apply the same
procedure to obtain the mass balance in mole units.
The chemical reaction rates per unit volume are:
 moles produced 
R1 & R2 =  
 cm3  sec
The two mass balance equations for the two species are:

c1 c2
+   N1   R1 +   N 2   R2
where N1 & N2 are
t t molar flux of 1 and 2

Sum the two equations to get the total mass balance

c Where
+   N1  N 2    R1  R2
But t
  N1  N2     c1v1  c2v2    cv*

Finally following eq. of continuity for the mixture

Since moles are generally not conserved, 
R1+ R2  0 unless one mole of species 2 is produced for +   cv*   R1  R2
t
every mole of species 1 consumed (or vice versa).
Equations of change for binary mixtures-4
c1
+   N1   R1
t

 x x x 
N1 = - c D12  1  1  1   x1  N1  N 2 
 x y z 

N1 = - c D12x1  x1  N1  N 2 

c1
+   N1   R1
t

 c c c 
N1 = - D12  1  1  1   x1  N1  N 2 
 x y z 

N1 = - D12c1  x1  N1  N 2 
 Equations of change for binary mixtures-7
Special case: No reaction & zero velocity

In this case, the mass balance equations are:

Which are now well known in the literature as the Fick’s second law of diffusion.
These equations are valid in:
1. Solids or stationary liquids
2. equi-molar, counter-diffusion of gas
Diffusion into a falling film -1

x All the examples:

z 1. Diffusion Stefan tube
2. Diffusion & heterogeneous reaction
3. Diffusion & homogeneous reaction
deal only with diffusion and bulk flow
induced by the mass transfer.

Now we deal with mass transfer caused

by diffusion and forced convection.
 Diffusion into a falling film -2
Shell mass balance
 Rate of   Rate of   Rate of mass   Rate of mass 
=      =  
 mass in   mass out   Production   accumulation 

W zN   W xN   W zN 

x ,1
x
z ,1
z
x ,1
x x
 W xN z ,1 
z z
0 0

where
Nx,1 is the molar flux in the x-direction
Nz,1 is the molar flux in the z-direction
In the limit of very thin shell

N x,1 N z ,1
 0 The specie 1, mass balance equation
x z
 Diffusion into a falling film -3
The molar flux in the x-direction

C1
N x ,1   D12  x1  N x ,1  N x ,2 
x

Since most gases dissolve sparingly in liquid, that is the bulk flow term
(second term) is negligible compared to the diffusive term, i.e.
C1
N x ,1   D12
x
The flux in the direction into the bulk liquid is controlled by diffusion.
The molar flux in the z-direction
C1
N z ,1   D12  x1  N z ,1  N z ,2  By definition of the flux:
z
N z ,1  C1vz ,1 ; N z ,2  C2vz ,2
C1
Rearrange the above equation as: N z ,1   D12  x1  C1vz ,1  C2vz ,2 
z
 Diffusion into a falling film -4
C1
N z ,1   D12  x1  C1vz ,1  C2vz ,2 
z

Compare the two terms

The flux of specie 1 in z The flux of specie 1 in z
direction by diffusion direction by convection

Can be neglected
Hence we end up with

N z ,1  x1  N z ,1  N z ,2   x1  C1vz ,1  C2 vz ,2  
C v
1 z ,1  C2 vz ,2 
x1  C1  C2 
 C1  C2 

C1 vz  x  Liquid bulk velocity

C1
Whereas we already have N x ,1   D12
x
 Diffusion into a falling film -5
our specie 1, mass balance equation becomes

N x,1 N z ,1  2C1 C
 0 D12 2  vz ( x) 1
x z x z

This is the typical form of diffusion

convection equation.

  g 2 cos    x  
2
Remember, the velocity distribution vz    1    
along a inclined plate  2      

  x 2    g 2 cos  
v z  vmax 1     vz  
     
max, at x = 0
 2 
 Diffusion into a falling film -6
Finally our specie 1, mass balance equation becomes

  x 2  C1  2C1
vmax 1      D12
     z x 2
convection term diffusion term
in z direction in x direction
All this equation says is that the amount of dissolved A diffusing in
the x direction is balanced by the amount of A carried downstream
by the fluid.

Physical constraints
1. At entrance of the liquid film: at z = 0; C1 = 0
2. At the gas-liquid interface: at x = 0; C1 = C10 (solubility), constant
for a given temperature and pressure in the gas phase.
3. At the liquid-solid surface, there is no penetration of mass in the x-
direction: at x =  ; Nx,1 = -D12 dC1 /dx = 0
 Diffusion into a falling film -7
Concentration Distribution
Mass balance equation together with the three boundary conditions can be
readily solved by the separation of variables method.
How do you expect the concentration to vary in the liquid film
Consider the low solubility and velocity distribution
This would then become the case of short contact time, i.e. dissolved gas
only travels a short distance into the bulk liquid
Because of the short contact time, The dissolved
molecules A will not travel far into the bulk, so:
1. they will experience only the velocity vmax
2. solid surface seems like too far away from them.

This assumption of short contact time leads to v(x) = vmax a constant

C1  2C1 at z = 0; C1 = 0
vmax  D12 2 at x = 0; C1 = C10
z x
at x →∞; C1 = 0
Matching boundary conditions, hence combination of variables
 Diffusion into a falling film -7
d 2 d 1.  = 0 = 1
 2 0 An ODE BCs’
d 2
d 2.  =  = 0
d d Solution of this ODE
 2  0 if  
d d 
  C1  exp( 2 )d  C2
0

  )d
2
exp( 
Using BCs’ to get 2
  1  0  1   )d  1  erf
2
exp(
the final result 
 exp( )d
2 0

0
 Diffusion into a falling film -8
Our new combined variable to transform PDE to ODE
x

4 D12 z
vmax

C1  x, z 
Finally our solution is  1  erf  erfc
C10

C1  x, z  x x
 1  erf  erfc
C10 4 D12 z 4 D12 z
vmax vmax

The molar flux into the bulk liquid can be calculated from Fick’s law:
C D12vmax  moles of A absorbed 
N x,1   D12 1 N x ,1 x 0  C10  interfacial area  time 
x x 0 z  
 Diffusion into a falling film -9
Observation
1. This molar flux is decreasing with respect to distance x as the
driving force is lower.
2. This flux is infinite at z = 0, because of the infinite driving force at
that point. Infinite flux? Does this worry us?

No it should not worry us, because we are interested in the amount

of moles absorbed over a certain length of the film, which is:

L L
D12vmax  moles of A absorbed 
M1  W  N x,1 x 0 dz  W  C10 dz  
0 0
z  time 

4D12vmax
M1  WL  C10
L
 Diffusion into a falling film -10
4D12vmax
M1  WL  C10
L
Observation
The mass transfer is proportional to: The exposure time is
1. solubility
2. square root of the diffusivity L
tex 
3. the width of the film vmax
4. square root of the length
It is inversely proportional to
5. square root of the exposure (contact)
time between the gas and liquid.
Another quantity of interest is average exit concentration. It is defined as
2
M 1  F  C1  F  WD  v  WD  vmax C1  M 1 F
3
3 D12 L 3 L vmax 3 exposure time
C1,exit  C10  C  C
 D 2 vmax
10
 D 2 D12
10
 diffusion time
 Gas Absorption From Rising Bubbles
Physical situation of gas absorption
vt from a rising bubble is very complex
Liquid B Result of the previous analysis can be
applied to this problem
D Gas A
Assumptions
1. Gas bubbles are of moderate size
Dissolved A 2. Liquid free of surfactants
3. Depth of penetration of dissolved gas is
small into the liquid due to small DAB
4. Case can be considered as gas
absorption in falling liquid film

The molar flux of gas dissolved into the bulk liquid

M1 4D12vmax
 N1 avg   C10
WL L
 Gas Absorption From Rising Bubbles-2
In context of rising bubble, can we do this variable transformation

Falling film Rising bubble

vmax vt
L D
where vt is the terminal velocity, and D is the bubble diameter.
Thus, the average molar flux out of the bubble is

4D12vt
 N1 avg  C10
D

How quick the bubble would deplete,

Do a mass balance around a bubble

Rate of moles reduced in bubble = Total molar rate flowing out of bubble sphere
 Gas Absorption From Rising Bubbles-3
Mass balance around the spherical bubble
d   D3 po 

dt  6 RT 
     D 2
 C10
4D12vt
D
po is the bubble pressure
For single isolated smallest bubbles, which are approximately perfect
spheres due to surface tension dominant effect of on their shape, Stokes
solution provides a reasonably accurate description of the terminal velocity
vt is a function of bubble diameter
g  D 2
vt 
18
Mass balance equation of a bubble becomes

dD 6  C10  4 D12 g 
  
dt D op RT   18

This equation describes how the bubble diameter changes with time.
 Gas Absorption From Rising Bubbles-4
A first-order ODE in terms of diameter D. The initial condition is:
at t = 0; D = Do (initial size)

Integrate to get
 C10  4 D12 g 
D  Do   t   
where  o
p RT   18

The time it takes for the bubble to disappear

1
t Do


The time it takes for the bubble to disappear is not of too much interest to
engineers.

What is of interest is the height required for the bubble to disappear

 Gas Absorption From Rising Bubbles-5
This height can be calculated from:
t*
H   vt dt
g  D2 0
vt 
18  C10  4 D12 g 
  
 o
p RT   18
D  Do   t

Therefore, the height calculated is Observation:

Height required to get rid of bubble
   g   po RT  52 is proportional to:
H      Do
 30 2   D12  C10  1. Do5/2
2. bubble pressure, po
3. square root of density difference
and is inversely proportional to:
4. square root of diffusivity
5. solubility
 Gas Absorption From Rising Bubbles-6
Example: The height required is = 2 cm
Cl2 gas absorption in water
D12 = 1.55 x 10-8 ft2/sec The height is 2 cm.
ρ = 59.4 lb/ft3 It is so short because of
μ = 6.73 x 10-4 lb/ft/sec the small size of the bubble
g = 32.17 ft/sec2
po = 1 atm
R = 0.73 atm-ft3/lbmole/R If the initial bubble size is 1 cm
T = 528 R
Do = 0.00328 ft = 0.1cm The new height required = 6.6 m
Cio = 0.01412 lbmole/ft3
This is to show that how quick the height
will increase with the bubble size.

Remember the functional dependence

on the bubble size is, D5/2
 Gas Absorption With Reaction in Agitated Tank-1
1. Each gas bubble is surrounded by a stagnant liquid
film of thickness , which is small relative to the
bubble diameter.
2. A quasi-steady concentration profile is quickly
established in the liquid film as bubble is formed.
3. The gas A is only sparingly soluble in the liquid, so
that we can neglect the convection term
4. The liquid outside the stagnant film is at a
concentration CAO which changes so slowly with
respect to time that it can be considered constant.
The shell balance around a bubble will lead to the following equation

d 2C A
DAB 2
 k C A  0
dz

Boundary Conditions Where

at z = 0; CA = CAo CAo = interfacial concentration of A in liquid phase
at z = ; CA = CA CA = liquid bulk concentration of A
Gas Absorption with Reaction in Agitated Tank-2
C A sinh  cosh    B  cosh  sinh  

C A0 sinh 
Where
  z , B  CA CAO and   k1 2 DAB

 = 0 for case without reaction

The liquid outside the stagnant

film is at a concentration CAO
which changes so slowly with
respect to time that it can be
considered constant

This assumption leads to the following mass balance

 Gas Absorption with Reaction in Agitated Tank-3
Mass diffusing through the stagnant film surrounding all the bubbles
in the tank = the moles of diffused gas consumed by chemical reaction
in the bulk of the tank liquid

dCA
S DAB  V k CA
dz z 
Total volume of liquid in tank

Total surface area of all bubbles Solve this equation by putting CA to get B

1
B
cosh   V S   sinh 

Now we are in a position to get the molar flux of A with chemical reaction
 dCA  DABCAo   cosh    B 
N A z 0    DAB     
 dz z 0    sinh  
 Gas Absorption with Reaction in Agitated Tank-4
Can we find the molar flux of A for the case of no reaction
We need to solve the specie shell balance equation with the same BC’s
but without the reaction term
d 2C A Changes to d 2C A Boundary Conditions
DAB 2
 k C A  0 DAB 2
0 at z = 0; CA = CA0
dz dz
at z = ; CA = CA

 CA   dCA  DABCAo
   B  1    N A no reaction    DAB   1  B 
 C Ao  no reaction  dz z 0  no reaction 

 dC A  DAB C Ao   cosh    B 
NA    DAB     
z  0, with reaction
 dz z 0    sinh  

Let us take the ratio of the two fluxes with and without reaction
  1 
N   cosh   
*

sinh   cosh   V S   sinh  

 Gas Absorption with Reaction in Agitated Tank-5
Dimensionless absorption rate
per unit area of interface, N*,
𝜙= 𝑘 ‴1 𝛿 2 Τ𝐷𝐴𝐵
increases with  for all finite
values of V/S
At very low values of  (for
very slow reactions) N*  0.
For this limiting situation liquid
is nearly saturated with gas, and
the driving force for absorption
is very small.

At large values of  the N* increases rapidly with  and becomes very nearly
independent of V/S. In this case the reaction is so rapid that almost all of the
dissolving gas is consumed within the film. B is almost zero, and the bulk of
the liquid plays no significant role.

In the limit as  becomes very large, N*  

 Gas Absorption with Reaction in Agitated Tank-6
𝜙= 𝑘 ‴1 𝛿 2 Τ𝐷𝐴𝐵
For intermediate values of  and for moderately large V/S, there is a
considerable range of  for which N* is very nearly unity.

In this region the chemical reaction is fast enough to have bulk concentration
equal to 0.
Whereas it is slow enough to have almost no effect on solute transport in film

Under such conditions a relative comparison of the volume of liquid in

tank and the volume of liquid in film becomes important

Large volume of bulk liquid offsets the fast volumetric reaction rate in the
film. In such a situation the absorption rate = physical absorption rate i.e
for k"' = 0

This behavior is frequently observed in practice, and operation under such

conditions has proven a useful means of characterizing the mass transfer
behavior of a variety of gas absorbers
 Solid Dissolution In Falling Liquid Film-1
Near wall
  g 
vz   y
   1. Liquid flows down the solid wall
 2. Solid wall is slightly soluble in liquid for
Parabolic
velocity
0<z<L
Insoluble profile of 3. Flow of liquid is laminar and steady
wall fluid B state for z  0
4. Fully developed i.e known laminar
Slightly soluble velocity profile
wall made of A 5. For short distances downstream, species
A will not diffuse very far into the
CA0 = saturation
L concentration
falling film
6. Hence A will be present only in a very
thin boundary layer near the solid
surface.

CA (y,z)
 Solid Dissolution In Falling Liquid Film-2
  g 2 cos    x  
2
Velocity profile for falling film case vz    1    
 2      

For our case cosβ = 1 and x =  - y hence

  g 2    y   y  
2
At and adjacent to the wall vz    2      
 2         
2
 y  y
    
   

  g 2    y   g
Hence the velocity profile becomes vz     2    ay a
 2       
 Solid Dissolution In Falling Liquid Film-3
A shell balance for the conditions given results in

 2C A CA
DAB  v ( y )
y 2 z
z

Boundary Conditions CA

1. at z = 0; CA = 0 3. at y   ; 0
y
2. at y = 0; CA = CA0
For short contact times
this BC changes to
at y  ; CA  0

This change of BC allows us to solve the PDE as ODE by making a new

dimensionless variable by the method of combination of variables to;
1

CA  a  3

new dimensionless variable  f     y 

C A0  AB 
9 D z
 Solid Dissolution In Falling Liquid Film-4
Thus our PDE transforms to the following ODE

d2 f 2 df Now the
 3 0 f (0)  1 and f ()  0
 2
 BCs’ will be


Solution of this ODE: f  C1  exp( 3 )d  C2
0

  ) d
3
when f (0)  1 then C2  1 when f ()  0 then C1  1 exp( 
0

 

   exp( )d   exp(  3 ) d

3
1
  )d  1
3
f  
exp(  f  0 0


 exp( ) d
3
  ) d
0 3
exp( 
0 0
 Solid Dissolution In Falling Liquid Film-5
  

  ) d   ) d   ) d
3 3 3
exp(  exp(  exp( 
  
f   

  43  0.893
 exp( ) d
3

CA  d  CA   
The local N Ay   DAB   DABC A0    
y 0 y y 0
d
  A0 
C y  y 0
molar flux
will be  exp( 3 )  a  
1 1

DABC A0  a 
3 3

  DABC A0        
  ( 4
3 )  9 DAB 
z   ( 4
3 )  9 DAB 
z
y 0

The total molar flux 1

2 DABC A0WL  a 
W L 3

from the whole surface WA    N Ay dz dx   

will be at y = 0 0 0
y 0 ( 73 )  9 DAB L 

where ( 73 )  34 ( 34 )  1.1907 (n  1)  n(n)

Steady State Diffusion in Fluids at Rest OR in Laminar Flow
Starting with the situation in the Stefan’s Tube Shell Balance leads to

dx1
N1  - c D12  x1  N1  N 2 
dz

dc1 c1
N1  - D12   N1  N 2 
dz c

c1,2
dc1
z
1 2

c1,1
N1c  c1  N1  N 2 
 
cD12 z1
dz

N1 cD12  N1  N1  N 2   c1,2 c  Physical system

N1 = ln  
N1  N 2 z2 - z1  N1  N1  N 2   c1,1 c  1. Liquid 1 in the tube
2. Gas 2 flows across tube’s mouth
c1,2 = 0
3. Gas 2 is non-soluble in liquid 1
N1 
P RT  D12  1 
ln  N2 = 0
o 
z2 - z1  1- p1 P 
Steady State Diffusion in Fluids at Rest OR in Laminar Flow
Molecular Diffusion in Gases
If we assume that ideal gas law is valid
0
c1 p1 n P
x1   c 
c P V RT

N1 PD12   N1  N1  N 2   P  p1,2
o

N1 = ln  
N1  N 2 RT  z2 - z1    N1  N1  N 2   P  p1,1
o 


N1 PD12   N1  N1  N 2    x1,2 
N1 = ln  
N1  N 2 RT  z2 - z1    N1  N1  N 2    x1,1 


In order to use these equations the relation between N1 and N2 must be known
Usually fixed by other considerations.
1 CH4  C + 2H2 2
N2 = -2 N1
under circumstances such that CH4 (1) diffuses
to the surface and H2(2) diffuses back, the N1
= -1
reaction stoichiometry fixes the relationship N1  N 2
Steady State Diffusion in Fluids at Rest OR in Laminar Flow
Steady State Diffusion of 1 through non-diffusing 2
Example,
Ammonia (1) absorbed from air (2) into water.
Air does not dissolve appreciably in water,
If we neglect the evaporation of water, only NH3 diffuses
Thus, N2 = 0, N1 = constant
N2 = 0 N1
=1
N1  N 2

N1 PD12   N1  N1  N 2   P  p1,2
o

N1 = ln  
N1  N 2 RT  z2 - z1    N1  N1  N 2   P  p1,1 
 o 

PD12  P  p1,2
o

N1 = ln  o 
P  p1,2
o o
= p2,2 P  p1,1
o o
= p2,1 o
p2,2  p2,1
o o
= p1,1  p1,2
o
RT  z2 - z1   P  p1,1 


 p  p 
o o

1,2 
PD12 Log mean pressure
N1 = p o
 p o
p2,o M =
2,2 2,1

RT  z2 - z1  p2,o M ln  p p 
1,1 o o
2,2 2,1 difference
Steady State Diffusion in Fluids at Rest OR in Laminar Flow
Steady State Equi-molar Counter Diffusion
This is a situation which frequently happens in distillation operations
N1 = -N2 = constant
D12 dp1 p1
  N1  N 2 
dc c
N1  - D12 1  1  N1  N 2  N1  -
dz c RT dz P

z2 p1,2
D12
z dz 
RTN1  dp
p1,1
1
1

N1 =
D12
RT  z2 - z1 
 p1,1  p1,2 
MASS TRANSFER COEFICIENTS
 MASS TRANSFER COEFICIENTS
N1 cD12  N1  N1  N 2   c1,2 c 
N1 = ln   N1 =N A
N1  N 2 z2 - z1  N1  N1  N 2   c1,1 c 
F
SOME VERY IMPORTANT CONSIDERATIONS
1. F = Characteristic of molecular diffusion called mass transfer coefficient.
a. Surfaces of mass transfer may not be plane
b. Diffusion path in the fluid may be of variable cross section,
2. NA = flux at the-interphase, or boundary, where mass enters or leaves the
phase for which F is the mass-transfer coefficient.
3. Hence concept of two mass transfer coefficients depending on the phase
4. NA = +ive when cA1 , is at beginning of the transfer path and cA2 at the end
 MASS TRANSFER COEFICIENTS
5. In any case, one of these concentrations will be at the phase boundary.
6. Definition of concentration of A in the fluid influences the value of F, and
this is usually established arbitrarily. E.g.
1. When a drop of water evaporates while falling through a large volume
of air, the concentration of diffusing substance in the fluid is usually
taken as the constant value found at large distances from the phase
boundary. If the fluid is not in a confining space

2. If the fluid is in a confining duct, so that the concentration is not

constant along any portion of the transfer path, then the bulk-average
concentration as found by mixing all the fluid passing a given point
S
1
cA  
ux S 0
u x c A dS

ux(z) = velocity distribution in gas across the duct ( = time average of ux

for turbulence)
𝒖x = bulk average velocity (volumetric flow rate / duct cross section)
S = duct cross-sectional area
 MASS TRANSFER COEFICIENTS
Two situations, namely equimolar counter-diffusion and transfer of one
substance through another which is not transferred, occur so frequently that
special mass-transfer coefficients are usually used for them.
Flux = (coefficient)(concentration difference)
Since concentration may be defined in a number of ways and standards have
not been established, we have a variety of coefficients for each situation:
Transfer of A through non-transferring B
NB = 0, NA/(NA+NB) = 1

kG  p A1  p A 2   k y  y A1  y A 2   kc  c A1  c A 2  gases
NA  
k x  x A1  x A 2   k L  c A1  c A 2  liquids
Equimolar counter-diffusion
NA = - NB, NA/(NA+NB) = 
kG  p A1  p A 2   k y  y A1  y A 2   kc  c A1  c A 2  gases
NA  
k x  x A1  x A 2   k L  c A1  c A 2  liquids
Relations Between Mass Transfer Coefficients
 Mass Transfer Coefficients In Laminar Flow
PRE-AMBLE
• In principle, mass-transfer coefficients for laminar flow are not needed as
molecular diffusion prevails
• All the equations determined early are sufficient to calculate the mass
transfer rates.
• However, a uniform method of dealing with both laminar and turbulent
flow is nevertheless desirable.
• Mass-transfer coefficients for laminar flow should be capable of
computation.
• However the mathematics involved if we do not take care of the
assumptions then the results obtained are somewhat short of reality.
• Lets solve one case in order to establish the method of solution for turbulent
flows. (This case we had already discussed)
Mass Transfer from a Gas into a Falling Liquid Film

z
y
Mass Transfer from a Gas into a Falling Liquid Film
• Liquid falling in a thin film in laminar flow down a
vertical flat surface while being exposed to a gas A,
which dissolves in the liquid.
• Liquid contains a uniform concentration cAo of A at top.
• Liquid surface, concentration of dissolved gas = cA,i , in
equilibrium with pressure of A in the gas phase.
• As cA,i > cAo, gas dissolves in the liquid.
• Problem is to obtain mass-transfer coefficient kL, with
which the amount of gas dissolved after the liquid falls
the distance L can be computed.
• We need a simultaneous solution of the equation of continuity for
component A with NS the equations describing the liquid motion.
• Simultaneous solution of this formidable set of PDEs’ is possible only by
applying several simplifying assumptions, namely:
1. There is no chemical reaction and steady state conditions prevail
2. Conditions do not change in the x direction hence a 2D problem
3. Rate of absorption of gas is very small, means that uz =0 hence 1D case
Mass Transfer from a Gas into a Falling Liquid Film
• Diffusion of A in the y direction is negligible in
comparison with the bulk (convective) movement of A
downward. Hence derivatives of concentration w.r.t y
are 0
• Physical properties (DAB,  and  are constant)
• Finally our equation becomes as done earlier
 2cA c A d 2u y
DAB  vy ( z)   g  0
z 2
y dz 2

• This simply states that any A added to the liquid running down at any
location z over an increment in y, got there by diffusion in the z direction.
• The equations of motion under these conditions reduce to
  g 2 cos    z     z 2  3  z 
2 2

vy    1     v y  vmax 1     v y  v y 1    
 2            2     
 3v y  
12 13
 3  where Γ is the mass rate of liquid flow
    2 
  g   g
per unit of film width in the x direction
Mass Transfer from a Gas into a Falling Liquid Film
Finally our PDE becomes
3   z   c A  2cA
2

v y 1      DAB 2
2      y z
Our boundary conditions are
1. At z = 0, cA = cA,i , at all values of y
2. At z = ,  cA/ z = 0 at all values of y, since no
diffusion takes place into the solid wall,
3. At y = 0, cA = cAo at all values of z.

Solution results in an infinite series giving cA for any z and y

c A ,i  c A , L
 0.7857e 5.1213  0.1001e 39.318  0.03599e 105.64  ........
c A ,i  c A , o
 c A 
 2
2 DAB L
Using the definition of
N A   DAB   
 k L c A ,i  c A , L 
3 v y
mass transfer coefficient  z  z 0
As per the nature of series describing cA, the derivative is undefined at z = 0.
Hence better to proceed with an average coeff.t for entire liquid-gas surface.
Mass Transfer from a Gas into a Falling Liquid Film
• Rate at which A is carried by liquid at any y, per unit
width in the x direction, product of average volumetric
flow rate and average concentration. Over a distance dy,
per unit width, therefore, the rate of solute absorption
v y dc A  k L  c A,i  c A  dy
is, in mol/time,

c A  c AL L L
dc A
v y    k L dy  kl ,av  dy
c A  c Ao  c A,i  c A  0 0

v y c A,i  c Ao
k L ,av  ln This defines the average coefficient
L c A ,i  c A , L

Now for small rates of flow or long times of contact of the liquid with
the gas (usually for film Reynolds numbers Re = 4Γ/ < 100), only the
first term of the series need be used. Giving
Mass Transfer from a Gas into a Falling Liquid Film
v y e5.1213 v y DAB
k L ,av  ln   0.241  5.1213   3.41
L 0.7857 L 
k L ,av
 Shav  3.41
DAB
where Sh represents the Sherwood number, the mass-transfer analog to the
Nusselt number of heat transfer
A similar development for large Reynolds numbers or short contact time gives

 6 DAB  
12
k L ,av  3 
12

k L ,av    Shav   Re Sc 
  L  DAB  2 L 

The product Re Sc is the Peclet number Pe.

Sc = Schmidt Number analogous to Prandtle number:
Ratio of momentum to concentration boundary layer thickness
Mass Transfer from a Gas into a Falling Liquid Film
Average kL’s can be used to find the total absorption rate
Average flux NA,av for the entire gas-liquid surface, per unit width, is the
difference in rate of flow of A in the liquid at y = L and at y = 0, divided by
N A   v y L   c A, L  c A , o 
the liquid surface.

As per the definition of mass

transfer coefficient this is also

N A  k L ,av c A,i  c A Mean 
For our case this kL is
found to be
   
k L ,av  v y L ln c A,i  c Ao c A,i  c A, L 
 c  c   c  c A, L 
Hence
c  cA   ln c  c c
A ,i Ao A ,i
A ,i M
 A ,i Ao A ,i  c A, L 
Experimental kL,av > theoretical values, even for low mass-transfer rates, due
to ripples & waves not considered in analysis which form at values of Re 25
Equations apply for Re up to 1200 if ripples are suppressed by wetting agents
Absorption for very soluble gases, produces important values of vz and this
will alter the velocity profile in the film.
 Equations of change for binary mixtures-2
The mass balance equations written in terms of the mass flux are not useful in
getting the concentration profiles.
SO
We have to use the relationship between the mass flux and the mass conc.

and get

Sum the two equations to get the total mass balance

 Equations of change for binary mixtures-8
The equation of continuity for each species

for i=1,2, ..., n.

Here, ri is the mass rate of reaction per unit volume, i.e.

Also, according to the definition

of the diffusive fluxes:

which is the law of conservation of mass.

Summing the individual mass balance equations wrt i=1,...,n, gives:

which is the continuity eqn for mixture For fluids of constant

mass density ρ, the continuity equation of the mixture is: