POLYMER PROCESS ENGINEERING

Mass transfer phenomenon in polymers: Laminar flow and boundary

layer conditions in mass transfer operations

Prof. Shishir Sinha

Department of Chemical Engineering

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 Topic previously covered
• Mass transfer coefficient
• Types of mass transfer coefficient
• Equimolar counter diffusion of two components
• Relation between mass transfer coefficient
• Mass transfer coefficient and film thickness
• Dimensionless numbers in mass transfer

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 Table of content
• Mass transfer coefficient in laminar flow
• Mass transfer in falling film
• Laminar falling film in inclined surface
• Mass transfer coefficient in turbulent flow
• Boundary layer theory
• Film theory

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 Mass transfer coefficient in laminar flow

• In principle we do not need to study the mass transfer coefficient in

laminar flow conditions.

• A uniform method of dealing both laminar and turbulent flow is

nevertheless desirable.

• We shall choose one relatively simple situation to

illustrate the general technique and to provide some
basis for considering turbulent flow.

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 Mass transfer coefficient in laminar flow
• Figure shows a liquid falling in a thin film in a
laminar flow down a vertical flat surface while
being exposed to a gas A, which dissolves in the
liquid.

• The liquid contains a uniform concentration CA0 of

A at the top.

• At the liquid surface the concentration of the

dissolved gas is CAi. in equilibrium with the pressure
of A in the gas phase, since CAi > CA0 gas dissolves in
the liquid.
Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Mass transfer coefficient in laminar flow
• The problem is to obtain the mass transfer
coefficient that is kL with which the amount of gas
dissolve after the liquid falls a certain distance L
can be computed.
• The problem is solved by simultaneous solution of
equation of continuity for the component A, with
the equation which describes the liquid motion that
is the Navier Strokes equations.
• The simultaneous solutions of the formidable set
of partial differential equations become possible
only when several simplifying assumptions are
made.
Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Mass transfer coefficient in laminar flow
• Consider the following equations of continuity derived for unsteady state
mass transfer:
C A C A C A C A   2C A  2C A  2C A 
Vx + Vy + VZ + = DAB  + +  + R A
… (1)
x y z t   x 2
y 2
z 2 

• For the present purpose, assume that

a) there is no chemical reactions in the systems, RA = 0
b) Conditions do not change in the x direction
(perpendicular to the plane of the paper. All
derivatives with respect to x should be 0.
c) Steady state condition prevail, C A = 0
t

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 Mass transfer coefficient in laminar flow
• Other assumptions are:
d) The rate of absorption of gas is very small this means that VZ in equation 1
due to diffusion of A is essentially zero.

e) Diffusion of A in the y direction is negligible in comparison with the

movement of A outward due to bulk flow,  2C A
DAB =0
y 2
f) The physical properties in this case (DAB, ρ, μ) are
constant. So, equation 1 reduces to:
C A  2C A
Vy = DAB …. (2)
y z 2

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 Mass transfer in falling film
• This states that 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 equation of motion under this condition will be again reduces to
 2V y
 +  .g = 0 ….. (3)
z 2
• The solution to equation 3 with the conditions Vy = 0 at z = δ and that
dVz/dz = 0 at z = 0, is well known

.g. 2   z 2 
Vy = 1 −    ….. (4)
2.     

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 Mass transfer in falling film
• The maximum velocity which occurs at z = 0 in equation 4

 .g. 2
…. (5)
V y ,max =
2.
• The bulk average velocity can be obtained as follows:
1 1
W
W
 
1  .g. 2   z 2 
V y ,avg =  Vy dA = 0 0 Vy dxdz = W 0 Vy dz =  0 2. 1 −   dz
A W     

 .g. 2
V y ,avg = ….. (6)
3.
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 Mass transfer in falling film
1
• The film thickness is then  =  3.V y ,avg   2 ….. (7)
  .g 
 
• Substituting equation 4 into equation 2 and then by using equation 6, we get:
3   z  2  C A  2C A
V y ,avg 1 −    = DAB ….. (8)
2      y z 2
• Which is to be solved under the following conditions
1. At z = 0, CA = CA,i at all the values of y.
2. At z = δ, C A z = 0 at all the values of y, since no
diffusion takes place into the solid wall.
3. At y = 0, CA = CA,0 at all values of z

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Mass transfer in falling film

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 Problem-1
Question: The absorption of pure carbon dioxide is carried out at 1
atmospheric pressure and at 25 degree centigrade by using water film flowing
down a vertical wall of 1 meter long. The water is essentially CO2 free
initially. The average velocity of the liquid is 0.2 meter per second. The
solubility of CO2 in water at 25 ᴼC and at 1 atmosphere is CA,i = 0.0336
kmol/m3
Calculate the film thickness and the rate of absorption of carbon dioxide ?

Use the following properties, DAB: 2 x 10-9 m2/s,

solution density ρ = 997 kg/m3and
viscosity μ = 8.95 x 10-4 kg/m.s at 25 ᴼC.

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 Laminar falling film in an inclined surface
• In any liquid flowing down a surface a velocity
profile is established with the velocity
increasing from 0 at the surface itself to a
maximum where it is contact with the
surrounding atmosphere.
Flow of liquid over a
surface
• The velocity distribution may be obtained in a
manner similarly used in connection with the
pipe flow but that the driving force is due to
gravity rather than the pressure gradient.

Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Laminar falling film in an inclined surface
• For the flow of a liquid of depth δ down a plain
surface of width w inclined at an angle θ to the
horizontal.

• A force balance in the Y direction (parallel to the

surface) may be written. Flow of liquid over a
surface
• In an element of length dy the gravitational force
acting on that part of the liquid which is at a
distance greater than z from the surface
= (δ-z)w.dy.ρ.g.sinθ

Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Laminar falling film in an inclined surface
• If the drag force of the atmosphere is negligible,
the retarding force for laminar flow is attributable to
the viscous drag in the liquid at a distance y from
the surface = μ.dVy/dz.wdy

Where, Flow of liquid over a

Vy is the velocity of the fluid at that position. surface

• Thus, at equilibrium
dVy
( − z )w.dy..g. sin  =  w.dy
dz
Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Laminar falling film in an inclined surface
• Since there will be normally no slip between the
liquid and the surface, then Vy = 0 when z = 0:
Vy
 .g . sin  z
0 dVy =  0 ( − z )dz
Flow of liquid over a
surface
 .g. sin   1 2
Vy =  z − z 
  2 

Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Laminar falling film in an inclined surface
• The mass rate of flow that is m of liquid down the surface can be calculated
as:

•  .g. sin   1 2
M = w z − z dz
0
  2 

•  2 g. sin    3  3 
M = w − 
  2 6 

•  2 g. sin  .w. 3
M=
3.
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 Laminar falling film in an inclined surface
•
• The average velocity of fluid is: M  .g. sin  2
V y ,avg = =
 .w. 3.
• For a vertical surface, sinθ =1
 .g. 2
V y ,avg =
3.
• The maximum velocity which occurs at the free surface is given by:
.g. sin  2
Vy =
2.
And this is 1.5 times the mean velocity of the liquid

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 Boundary layer theory in mass transfer
• An exact solution can be obtained for the
hydrodynamic boundary layer for isothermal
laminar flow past a plate.

• An extension of the Blasius solutions can be Laminar flow of fluid passes a

extended to derive an expression for convective flat plate and concentration
heat transfer. boundary layer

• In the analogous manner we can use the

Blasius solutions for convective mass transfer
as well for the same geometry and laminar flow.

Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Boundary layer theory in mass transfer
Here,

• CA∞ = is the concentration of A in the fluid

approaching the plate.
• CAS = is the concentration of A in the fluid Laminar flow of fluid passes a
adjacent to the surface flat plate and concentration
• We start with the differential mass balance and boundary layer
simplifying it for steady state process where,
C A
=0
t
Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Boundary layer theory in mass transfer
• Flow only in the x and y directions, so Vz = 0
and neglecting diffusion in the x and z directions
to give:

C A C A  2C A ….(13)
Vx + Vy = DAB Laminar flow of fluid passes a
x y y 2 flat plate and concentration
boundary layer
• The momentum boundary layer is very similar,
So:
Vx Vx   2Vx
Vx + Vy = …. (14)
x y  y 2
Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Boundary layer theory in mass transfer
• The thermal boundary layer is also similar:
T T K  2T
Vx + Vy = …. (15)
x y  .C P y 2
• The dimensionless concentration boundary Laminar flow of fluid passes a
conditions are flat plate and concentration
Vx T − TS C − C AS boundary layer
= = A =0 at y = 0 … (16)
V T − TS C A − C AS

Vx T − TS C − C AS at y = ∞ …. (17)
= = A =1
V T − TS C A − C AS

Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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Boundary layer theory in mass transfer

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 Boundary layer theory in mass transfer
• The relations between the thickness δ of the
hydrodynamic and the δc of the concentration
boundary layer, where the NSc ≠ 1.0 is


1
= N Sc3 ….. (23) Laminar flow of fluid passes a
C flat plate and concentration
boundary layer
• As a result, the equation for local convective
mass transfer coefficient is
1 1
kC' x
= N Sh, x = 0.332N Re,
2 3
x N Sc
…. (24)
DAB
Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Boundary layer theory in mass transfer
• We can obtain the mean mass transfer
coefficient kC‘ from x = 0 to x = L for a plate of
width b by integrating as follows:
L
b
kC =  ….. (25)
' ' Laminar flow of fluid passes a
k C dx flat plate and concentration
b.L 0 boundary layer
• The result is
1 1
kC' .L
= N Sh,L = 0.664N Re,
2 3
L N Sc
….. (26)
DAB

Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
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 Problem-2
Question: A large volume of pure water at 25 ᴼC is flowing parallel to a flat
surface of solid benzoic acid, where L is 0.244 m in the direction of flow. The
water velocity is 0.061 m/s. The solubility of benzoic acid in water is 0.02948
kmol/m3. The diffusivity of benzoic acid is
1.245 x 10-9 m2/s. Calculate the mass transfer coefficient kC' and the flux NA.
Given that μ = 8.71 x 10-4 kg/m.s and ρ = 996 kg/m3

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 Mass transfer coefficient in turbulent flow
• There are many theories which attempt to interpret or explain the behavior
of mass transfer coefficient.

Such as:
a) Film theory Nernst (1904)
b) Penetration theory Higbie (1935)
c) Surface-renewal theory Danckwerts (1951)

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 Film theory
• The Nernst postulated that near the interface
there exist or stagnant film.

• The stagnant film which is hypothetical since we

really do not know the details of the velocity
profile near the interface.

• The basic concept : the resistance to diffusion

can be considered equivalent to that in the
stagnant film of a certain thickness.

Wankat P. C., “Separation Process Engineering”, 2nd Ed., 2006, Prentice Hall.
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 Film theory
• Mass transfer occur by molecular diffusion
through the fluid layer at phase boundary that
is at solid wall. Beyond this film the
concentration is homogeneous and is CAb.

• Mass transfer through the film occurs at Concentration profile with

steady state. stagnant film

• Flux is low and mass transfer occurs at low

concentration. Hence, − DAB dC A
NA =
dz
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 Film theory
• The steady state mass balance over an
elementary volume of thickness ΔZ.
• Rate of input of solute at:Z = N A
Z

• Rate of output of solute at: Z + Z = N A Z +Z

• Rate of accumulation = 0
= rate of input-rate of output
• Therefore,
At steady state:
NA Z
− NA Z + Z
=0
Brown G. G. and Associates, “Unit Operations”,1995, CBS Publishers
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 Film theory
Consider

Then,
….. (27)
dN A
=0
dz
….. (28)
d  − D AB dC A 
 =0
dz  dz 
d 2C A ….. (29)
− D AB 2
=0
dz
d 2C A ….. (30)
2
=0
dz
Brown G. G. and Associates, “Unit Operations”,1995, CBS Publishers
43
 Film theory
• Integrating equation 3 for the following boundary
conditions
CA = CA,i when Z = 0
CA = CAb when Z = δ
C A = C A,i − (C A,i − C Ab )
We have now: Z

• Hence, according to film theory
Concentration profile in stagnant film is linear
• Molar flux through film, NA: dC
N A = − DAB A
Therefore, dz Z =0
D AB (C A,i − C Ab )
NA =
 … (31)
Brown G. G. and Associates, “Unit Operations”,1995, CBS Publishers
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 References
• Fundamental of Heat and Mass Transfer, Incropera and Dewitt, 5th Edn.,John Wiley & Sons.
• Basmadjian D., “Mass Transfer and Separation Processes: Principles and Applications”,
2007, CRC Press
• Treybal R.E., “Mass Transfer Operation”, 3rd Ed., 1980, McGraw Hill.
• McCabe W.L., Smith J.C. and Harriott P., “Unit Operations of Chemical Engineering”, 6th
Ed., 2001, McGraw Hill
• Foust A. S., Wenzel L. A., Clump C. W., Maus L. and Andersen L.B., “Principles of Unit
Operations”, 2nd Ed., 2008,Wiley-India.
• Brown G. G. and Associates, “Unit Operations”,1995, CBS Publishers.
• Wankat P. C., “Separation Process Engineering”, 2nd Ed., 2006,
Prentice Hall.
• R. Taylor and R. Krishna, Multicomponent Mass Transfer, John
Wiley & Sons Inc. Edition 1st, 1993
• J. A. Wesselingh and R. Krishna, Mass Transfer in Multicomponent
Mixtures, Delft Academic Press. Edition 1st, 2000.
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Thank You

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