Mass Transfer 2019

MASS TRANSFER
 MASS TRANSFER OPERATIONS BY TREYBAL

 TRANSPORT PHENOMENA By BIRD
 HEAT & MASS TRANSFER A PRACTICAL APPROACH
BY CENGEL
MODES OF MASS TRANSFER
MASS TRANSFER MODES
DIFFUSION CONVECTION
MOLECULAR KNUDSEN, ONLY IN GASES
Molecular diffusion, simply called diffusion.

Diffusion explains the net flux of molecules from a region of higher
concentration to one of lower concentration
1. Thermal motion of all (liquid or gas) particles at temperatures above 0K.
2. Rate of this movement is a function of T,  and size of the particles.
3. Once concentrations are equal the molecules continue to move.
4. As there is no concentration gradient, process of molecular diffusion
ceases and now governed by the process of self-diffusion, resulting in a
gradual mixing of material, such that the distribution of molecules is
uniform, resulting in "dynamic equilibrium".
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)
KNUDSEN, ONLY IN GASES
Diffusion, when 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
If the pore diameter is smaller than the mean free path of the diffusing gas
molecules and the density of the gas is low, the gas molecules collide with the
pore walls more frequently than with each other.
Molecules do not interact with one another, so that they move in straight lines
between points on the pore channel surface.
• Knudsen number Kn, a good measure of relative importance of Knudsen
diffusion.
• Kn >> 1 indicates Knudsen diffusion is important. In practice, Knudsen
diffusion applies only to gases as liq is very small, typically = diameter of
the molecule itself. 𝜆
KNUDSEN NUMBER K 𝑛 =
𝐿
SURFACE DIFFUSION
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
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 ‘j’
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
This mass average
 total mass   distance  velocity of mixture is the
Note that v    
 volume   time  local velocity 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
c k 1 c k 1
mixture is defined as: 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*
MASS AND MOLAR FLUXES RELATIVE TO STATIONARY COORDINATES
Total
 mass of species j   distance 
Mass flux nj   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  cjv 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’
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 velocity
Bulk velocity
Specie There are two diffusion
convection velocities. In applications
velocity Mixture = v
where we deal with molar
flow, the diffusion velocities
Species -1= vj with respect to v* will be used
Diffusion Convection
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 k
n 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
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
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 only
• 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
n i  ρi vi  i ρvi n   ni  i vi  i  vi  v
i 1 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 n k  jk   k v
n
J A  N A  xA  N B  N B 
J k  ck vk - ck v  N k  ck v  N k  xk  N k
k 1 N A  J A + cv*
(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 d x1

an isobaric and isothermal system is:
J1  cD12
dz
Similarly, we can write an equation d x2
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 the procedure 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 A z  - 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
N A  - c DAB x A  x A  N A  N B  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
Equations of change for binary mixtures-1
Control volume, x, y,  z through which a
mixture including component A is flowing
Conservation of a given species A,
Should include a term that accounts for the production
or disappearance of A by chemical reaction within the
volume
General relation for a mass balance of species A
for our control volume
𝑛𝑒𝑡 𝑟𝑎𝑡𝑒 𝑜𝑓
𝑛𝑒𝑡 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛
𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
𝑒𝑓𝑓𝑙𝑢𝑥 𝑜𝑓 𝐴 + - 𝑜𝑓 𝐴 =0
𝑜𝑓 𝐴 𝑤𝑖𝑡ℎ𝑖𝑛
𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝐶𝑉 𝑤𝑖𝑡ℎ𝑖𝑛 𝑡ℎ𝑒 𝐶𝑉
𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝐶𝑉
Net rate of mass efflux from the CV across its control surfaces
in the x, y & z direction:
N A, x yz x x  N A, x yz x N A, y xz  N A, y xz N A, z xy z z  N A, z xy z
y y y
c A
Rate of accumulation of A in CV xyz
t
Specie ‘A’ produced within CV by a chemical reaction at a rate RA, (moles of
‘A’ produced)/(volume)(time)
Should include a term that accounts for the production or RA xyz
disappearance of ‘A’ by chemical reaction within the volume
Dividing by the volume, (x y z) and take limits x, y, z goes to zero
N A, x N A, y N A, z c A
    RA  0
x y z t
Equation of continuity for component ‘A’. NA,x; NA,y; and NA,z are the
rectangular components of the mass flux vector, NA,
c A
  NA   RA  0
t
cB
Equation of continuity for component ‘B’   NB   RB  0
t
  c A  cB 
For the mixture of ‘A’ and ‘B’    N A  NB     RA  RB   0
t
For a binary mixture of ‘A’ and ‘B’
N A  N B  c Av A  cB vB  cV nA  nB   Av A   B vB  V
c A  cB  c RA   RB  A  B  
c 
Only when stochiometrically A B   cV  0   V  0
t t
Special Forms of The Differential Mass-transfer Equation

Replace flux, NA, by the total mass flux expression in terms of Fick’s Law
N A  cDAB x A  x A  N A  N B   J A  cv*
c A  A
   J A      c A v*    RA  0    jA       A v    rA  0
t t
If density,  and diffusion coefficient, DAB can be assumed constant
0 c c A
cDAB  x A  c A  V  V c A  A  RA  0
2
V c A   cDAB  2 x A  RA
t t
If  and DAB are constant and there is no production term, RA = 0,
c c A Dc A
V c A  A  cDAB  2 x A  RA V c A   cDAB  2 x A  cDAB  2 x A
t t Dt
Dc A DT
 DAB  2 c A   2T
Dt Dt
When there is no fluid motion, V = 0, no production, RA = 0,  & D are const.
c A
 DAB  2 c A
t
For steady state and  & D are const. V c A  DAB  2 c A  RA
For steady state,  & D are const. and RA = 0 V c A  DAB  2 c A
For non-flow steady state,  & D are const. and RA = 0  2cA  0

If  and DAB are constant and there is no production term, RA = 0,
c A Dc A
V c A   cDAB  2 x A  DAB  2 c A
t Dt
Also called Fick’s second law of diffusion

Explicitly in rectangular coordinates
c A   2cA  2cA  2cA 
 DAB  2  2  2 
t  x y z 
Explicitly in cylindrical coordinates

c A   2 c A 1 c A 1  2 c A  2 c A 
 DAB  2   2  2 
t  r r r r  2
z 
Explicitly in spherical coordinates

c A  1   2 c A  1    cA  1  2cA 
 DAB  2  r  2  sin   2 2 2 
t  r r   r  r sin       r sin    
General differential equation for mass transfer of component A
Explicitly in rectangular coordinates

c A  N A, x N A, y N A, z 
     RA
t  x y z 
Explicitly in cylindrical coordinates

c A  1  1  N A, N A, z 

t  r r
 rN A, r  
r 

z    RA
Explicitly in spherical coordinates

c A  1  2  1 N A, 

t  r 2 r
 r N A,r   r sin    N A, sin    r sin     RA
1

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.

Step 7: Physical constraint; The two boundary conditions are:
Vapor pressure at gas-liquid
o
p surface else partial pressure
at z  z1 ; x1  x1,o 
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 
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.
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
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
r
Sparingly soluble sphere surrounded by infinite fluid
r Sphere (species 1) dissolves in fluid 2 with solubility of C10
Mass balance eq. around thin shell at r, having thickness r:
 4 r N    4 r N 
2
1
r
2
1
r r
0 0
2R Divide by 4πΔr, and take the limit that Δr approaches zero

lim   
r N  4 r N 
2 2

d 2

1 1
r 0
r r r
 r N1  0
r dr
Using the species balance eq.
0 0 0 0
c A  1  2  1 N A, 

t  r 2 r
 r N A,r   r sin    N A, sin    r sin     RA
1

d 2
dr
 r N A, r   0
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
Another way to handle NB
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. Make smaller object (size reduction) If we define the mass transfer
2. increase solubility (T/P effect) coefficient as:
3. larger diffusivity
N1 r R  km  CIO  0
Matching this with the
solution obtained from km  2 R 
2
first principles, we get: D12
this is known as the
Schmidt number,
Note similarity of Nu = hD/K = 2 which is equal to 2 for
for heat transfer from sphere in stagnant environment
stagnant medium
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
Another way to handle NB
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
0 0 0 0
c A  N A, x N A, y N A, z  dN1 which simply states that the molar
     RA  0
t  x y z  dz flux is constant along the tube
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  
 
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
 
 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

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

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
 
 
 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 
  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 
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
@ 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

=      =  
SN1 z  SN1 z z   S z  kC1  0

Negligible because
dN1 A is sparingly
  kC1  0
dz soluble in B
dx1
Step 6:Apply the Fick’s law N1  - c D12  x1  N1  N 2 
dz
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
0 0 Specie 1 is consumed
c d 2C1 d 2C1
  cD12x1    c1V  1  R1  0 D12  R1  D12  k1C1  0
t dz 2
dz 2
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
Using the Fick’s law at this point (z = L) dC1
at z  L; N1 z  L   D12 0
dz zL
 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 
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

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

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

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.
Shell mass balance
=      =  
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
c A  N A, x N A, y N A, z  N x,1 N z ,1
     RA  0
t  x y z  x z
The specie 1, mass balance equation

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
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
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 
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
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
4D12 z d 2 d
  f  x, z , D12 , vmax  x  2 0
vmax d 2
d
d 1.  = 0 = 1
 2  0 if   d An ODE BCs’
d d 2.  =  = 0

Solution of this ODE   C1  exp( 2 )d  C2
x 0
  2
exp( x )dx x erfc x  1  erf x
2
erf x     erf 0  0, erf   1
0 2

exp( x )dx

 exp( x )dx erf 2  0.99
2 0
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
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:
C1
exp  u 
d 2 2 du
N x,1   D12 erf u 
x x 0 dx  dx
D12vmax  moles of A absorbed 

N x ,1 x 0  C10  interfacial area  time 
z  
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
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
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
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

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
Example: If bubble diameter = 1 mm
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

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  
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  

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*  

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)
  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       
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
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
  
  ) 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 
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 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 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
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
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
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
• 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
• 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
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.
• 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
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 
 
Sc = Schmidt Number analogous to Prandtle number: Sc  
 DAB DAB
The product Re Sc is the Peclet number Pe.
Ratio of momentum to concentration boundary layer thickness OR
Ratio of viscous diffusion rate to the mass diffusion rate (at molecular level)
Average kL’s can be used to find the total absorption rate
Average NA,av for entire gas-liquid surface, per unit width, is difference in
rate of flow of A in the liquid at y = L and at y = 0, divided by liquid surface
area.
 v W c v  Wc 
NA       v y L   c A, L  c A , o 
y A, L y A,o
 WL WL 
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 
c  cA   ln c  c c
A ,i Ao A ,i
Hence 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.
INTRODUCTION TO TURBULENCE
WHY STUDY TURBULANCE
Turbulent behavior understanding of flowing fluids is one of the most intriguing,
frustrating—and important—problems in all of classical physics
A fact: Most fluid flows are turbulent & same fluids occur on all micro/macroscopic
scales throughout known universe from;
1. Interior of biological cells, to circulatory & respiratory systems of living creatures
2. Countless technological devices and household appliances of modern society
3. Geophysical & astrophysical phenomena including planetary interiors, oceans and
atmospheres, Even in galactic and even super-galactic scales
Recently proposed that turbulence is responsible for the present form of the Universe
during the very earliest times following the Big Bang
Despite the widespread occurrence of fluid flow, and the ubiquity of turbulence, the
“problem of turbulence” remains to this day the last unsolved problem of classical
mathematical physics
Turbulence has been studied by many of the greatest physicists and engineers of the
19th and 20th Centuries.
Understanding in complete detail on how or why turbulence occurs and how it can be
predicted with any degree of reliability, even in very simple flow situations
HENCE, study of turbulence is motivated both by its inherent intellectual challenge
and by the practical utility of a thorough understanding of its nature
Da-Vinci definition of Turbulence (TURBOLENZA)
The smallest eddies are almost numberless, and large things
are rotated only by large eddies and not by small ones, and
small things are turned by small eddies and large
Richardson 1922, definition of Turbulence

Big whorls have little whorls,
which feed on their velocity;
And little whorls have lesser whorls,
And so on to viscosity.
T. von K´arm´an quotes G. I. Taylor’s definition of Turbulence

Turbulence is an irregular motion which in general makes its appearance in fluids,
gaseous or liquid, when they flow past solid surfaces or even when neighboring
streams of the same fluid flow past or over one another
Hinze definition of Turbulence

Turbulent fluid motion is an irregular condition of the flow in which the various
quantities show a random variation with time and space coordinates, so that
statistically distinct average values can be discerned
None of these definitions offers any precise characterization of turbulent flow such
that one can predict when turbulence will or will not occur, or what would be its
extent and intensity, a priori, on the basis of specific flow conditions
Lack of precision has to some extent contributed to the inability to solve turbulence
problem: if one does not know what turbulence is/or under what circumstances it
occurs, it is unlikely that one can say much of it in a quantitative sense
Chapman and Tobak described the evolution of our understanding of turbulence in
terms of three overlapping eras: i) statistical, ii) structural and iii) deterministic
One of the latest definition of Turbulence
Turbulence is any chaotic solution to the 3-D NS equations that is sensitive to initial
data and which occurs as a result of successive instabilities of laminar flows as a
bifurcation parameter is increased through a succession of values
Turbulent flow can be expected to exhibit all of the following features
1. Disorganized, chaotic, seemingly random behavior;
2. Non-repeatability (i.e., sensitivity to initial conditions);
3. Extremely large range of length & time scales (continuum hypothesis applicable);
4. Enhanced diffusion (mixing) and dissipation (both of which are mediated by
viscosity at molecular scales)
5. 3-D, time dependence and rotationality (hence, potential flow cannot be turbulent)
6. Intermittency in both space and time
• Considering a turbulent flow in a tube with a constant imposed pressure gradient
• If at one point in the fluid we observe one component of the velocity as a function
of time, we find that it is fluctuating in a chaotic fashion
• Fluctuations are irregular deviations from a mean value
• Actual velocity can be regarded as sum of the mean value 𝑣ҧ and the fluctuation 𝑣 ′
The Reynolds decomposition vz  vz  vz

t  0.5t
o T
1 1
Time wise mean of a turbulent function v(x, y, z, t) vz   vz  s  ds   vz  t  dt
over a large number of fluctuations is defined as; to t 0.5to T 0
• T or to is an averaging period to be longer than any significant period of fluctuations
• Known as time-smoothed velocity, independent of time, but depends on position
• Averaging period for turbulent gas & water flows, of T = 5s is usually quite adequate
Time-smoothed velocity, also known as steadily driven turbulent flow
Same comments for velocity can also be made for pressure
Verify that the following relations are true (Assignment)
   
vz  0 vz  vz vz vz  0 vz  vz vz  vz
x x t t
T
1
vz    vz  vz  dt  vz  vz  0

T 0
However, vz 2  0 v 2 v A measure of the magnitude of the turbulent
z z fluctuations
• This quantity, known as the intensity of turbulence

• May have values from 1 to 10% in the main part of a turbulent stream
• May have values of 25% or higher in the neighborhood of a solid wall
• Hence, these are not necessarily tiny disturbances; sometimes the fluctuations are
actually quite violent and large, similarly v v  0
x y
• Local motions in the x and y directions are correlated
• Fluctuations in the x direction are not independent of the fluctuations in the y
direction
• These time-smoothed values of the products of fluctuating properties have an
important role in turbulent momentum transfer as well as heat and mass transfer
Mass Transfer Analogies
Prandtl assumed that for turbulent flow in viscous sublayer where ED and EH were
both zero and a turbulent core molecular diffusivities were negligibly important.
Resulting analogy between heat and momentum transfer, as we might expect, is
useful only for cases where Pr =1
However, a remarkably simple empirical modification of Prandtl’s analogy by
Colburn, represents the data even for large Pr very well (Colburn analogy)
1
hav 2 f
  2 St H ,av Pr 3  jH
2
St H ,av
C p u x  Pr 3
hav
St H ,av Pr  Pr 3  jH  f    Re 
2 2
3 1
C pux  2
For mass transfer Chilton Colburn analogy, agree quite well with experimental data
Fav 2 3
St H ,av Sc  Sc  jD  f    Re 
2
3 1
2
cu x
Analogies can also be developed between the transport phenomena from velocity,
concentration, and temperature distributions from which the eddy diffusivities can
be obtained. Some simple analogies developed correlations are
f 2
St H ,av 
1.20  11.8  f 2     1 3
0.5
Pr 1 Pr
f 2
St D ,av 
1.20  11.8  f 2   Sc  1 Sc 1 3
0.5
useful for Pr = 0.5 to 600 and Sc up to 3000.
Experimental data have come from so-called wetted wall towers and flow of liquids
through soluble pipes.
A volatile pure liquid flows down the inside surface of a circular pipe while a gas is
blown upward or downward through the central core.
Measuring rate of evaporation of the liquid into the gas stream over the known surface
permits calculation of the mass-transfer coefficients for the gas phase.
Use of different gases and liquids provides variation of Sc 0.6 to 2.5.
Sherwood and Gililand covered values of Re 2000 to 35000 and gas pressures
from 0.1 to 3 atm.
Linton and Sherwood caused water to flow through a series of pipes made by
casting molten benzoic acid and other sparingly soluble solids.
In this way the Sc was increased to 3000
Those data are empirically correlated by
Shav  0.023Re0.83 Sc1 3 data for gases only are better correlated with
0.44 replacing 1/3 as the exponent on Sc,
For Re 5000 to 200000, the friction factor in smooth pipes can be expressed as
1
2f  0.023Re 0.2
Shav
Combining the two equation give
1.03
Sc 23
 1
2 f
Re Sc
As turbulence intensity increases, theory predicts that the exponent on Re should
approach unity. Hence, for liquids with Sc > 100,
Shav  0.0149 Re0.88 Sc1 3

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

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:

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MASS TRANSFER

 MASS TRANSFER OPERATIONS BY TREYBAL

MOLECULAR KNUDSEN, ONLY IN GASES

Molecular diffusion, simply called diffusion.

IN GENERAL MASS TRANSFER BY DIFFUSION IS MORE COMPLICATED THAN

Diffusion, when scale length of a system is comparable to or smaller than the

A process involving the motion of adatoms, molecules, and atomic

The word “solution” means one phase

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

‘velocity of species j,” does not mean

THE LOCAL MOLAR AVERAGE VELOCITY IS DEFINED AS

The local molar c v k k c v k k n

 total moles   distance 

It is the local molar rate through a unit cross

which is the total mass of

which is the total moles of

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

 diffusion velocities of   diffusion velocities of 

Mass fluxes relative to the Molar fluxes relative to the

PROPERTIES OF DIFFUSIVE FLUXES

This equation means that within the movement of the bulk

Hence, for a binary mixture

TWO SPECIES MOVE IN THE OPPOSITE DIRECTION

THIS GIVES RISE TO THE CONCEPT OF

This equation simply states that the diffusive n

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

Mass Flux of component i Total Mass Flux

 = mixture mass density

Mathematical Interpretation of Experience

The basic equation for Fick’s law for d x1

State Order of magnitude (cm2/sec)

Solid 110-12 - 110-7

Temperature and pressure dependence

or in three dimensional coordinates

Generally, there are five boundary conditions:

A non-reacting system A reacting system

Special Forms of The Differential Mass-transfer Equation

For steady state and  & D are const. V c A  DAB  2 c A  RA

For steady state,  & D are const. and RA = 0 V c A  DAB  2 c A

For non-flow steady state,  & D are const. and RA = 0  2cA  0

Also called Fick’s second law of diffusion

Explicitly in cylindrical coordinates

Explicitly in spherical coordinates

Explicitly in rectangular coordinates

Explicitly in cylindrical coordinates

Explicitly in spherical coordinates

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

SN1 z  SN1 z z  0  0

Step 6: Apply the Fick’s law

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

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

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

Solving for K1 and K2, we get

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

Step 9: Molar flux

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

diffusive flux convective flux

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

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

Reasons for this extremely long time required

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

Then the evaporation rate N1 

Compare the two relations in context with the previous example

T oC N1 / For low temperature, the convective