Molecular and

UNIT 12 MOLECULAR AND TURBULENT Turbulent Diffusion

DIFFUSION
Structure
12.1 Introduction
Objectives
12.2 Mass Transfer in Laminar Flow in a Tube
12.2.1 Mass Transfer for Laminar Flow Inside Pipes
12.2.2 Mass Transfer for Turbulent Flow Inside Pipes
12.3 Laminar Flow and Boundary Layer Theory in Mass Transfer
12.4 Prandtl Mixing Length and Turbulent Eddy Mass Diffusivity
12.5 Diffusion in a Laminar Falling Film
12.6 Mass Transfer for Flow Outside Solid Surfaces
12.6.1 Mass Transfer in Flow Parallel to Flat Plates
12.6.2 Mass Transfer for Flow Past Single Spheres
12.7 Mass Transfer to Packed Beds
12.8 Mass Transfer for Flow Past Single Cylinders
12.9 Liquid Metal Mass Transfer
12.10 Mass Transfer to Suspensions of Small Particles
12.10.1 Mass Transfer to Small Particles < 0.6 mm
12.10.2 Mass Transfer to Large Gas Bubbles > 2.5 mm
12.10.3 Mass Transfer to Particles in Transition Region
12.10.4 Mass Transfer to Particles in Highly Turbulent Mixers
12.11 Summary
12.12 Key Words
12.13 Answers to SAQs

12.1 INTRODUCTION
When a fluid is flowing in a laminar flow and mass transfer by molecular diffusion is
occurring, the equations are very similar to those for heat transfer by conduction in
laminar flow. The phenomena of heat and mass transfer are not always completely
analogous since in mass transfer several components may be diffusing. Also, the flux of
mass perpendicular to the direction of the flow must be small so as not to distort the
laminar velocity profile.
In theory it is not necessary to have experimental mass-transfer coefficient for laminar
flow, since the equation for momentum transfer and for diffusion can be solved.
However, in many actual cases it is difficult to describe mathematically the laminar flow
for geometries, such as flow past a cylinder or in a packed bed. Hence, experimental
mass-transfer coefficients are often obtained and correlated. Simplified theoretical
derivations will be given for few cases in laminar flow. A brief introduction on turbulent
mass transfer will also be presented for few cases.
Objectives
After studying this unit, you should be able to
• recognise the laminar and turbulent mass transfer processes,
• formulate and evaluate various mass transfer processes in laminar and
turbulent flow, and 25
Mass Transfer • know the various types of mass transfer processes such as mass transfer in a
falling film, around a sphere, etc.

12.2 MASS TRANSFER IN LAMINAR FLOW IN A TUBE

We consider the case of mass transfer from tube wall to a fluid inside in laminar flow,
where, for example, the wall is made of solid benzoic acid which is dissolving in water.
This is similar to heat transfer from a wall to the flowing fluid where natural convection
is negligible. For fully developed flow, the parabolic velocity is

⎡ ⎛ r ⎞2 ⎤ ⎡ ⎛ r ⎞2 ⎤
vx = vmax ⎢1 − ⎜ ⎟ ⎥ = 2vav ⎢1 − ⎜ ⎟ ⎥ . . . (12.1)
⎢⎣ ⎝ R ⎠ ⎥⎦ ⎢⎣ ⎝ R ⎠ ⎥⎦

where vx is the velocity in the x-direction at the distance r from the centre. For
steady-state diffusion in a cylinder, a mass balance can be made on a differential element
where the rate in by convection plus diffusion equals the rate out radially by diffusion
give

∂c A ⎛ 1 ∂c A ∂ 2 c A ∂ 2 c A ⎞
vx = DAB ⎜⎜ + + ⎟ . . . (12.2)
∂x ⎝ r ∂r ∂r 2 ∂x 2 ⎟⎠

∂ 2cA
Then, = 0 if the diffusion in the x direction is negligible compared to that by
∂x 2
convection. Combining Eqs. (12.1) and (12.2), the final solution is a complex series
similar to the Graez solution for heat transfer and a parabolic velocity profile.
If it is assumed that the velocity is flat as in rodlike flow, the solution is more easily
obtained. A third solution, called the approximate Leveque solution, has been obtained,
where there is a linear velocity profile near the wall and the solute diffuses only a short
distance from the wall into the fluid. This is similar to the parabolic velocity profile
solution at high flow rates.

12.2.1 Mass Transfer for Laminar Flow Inside Pipes

Dvρ
When a liquid or a gas is flowing inside a pipe and the Reynolds number Re = is
μ
below 2100, laminar flow occurs. Experimental data obtained for mass transfer from the
W
walls for gases are plotted in Figure 12.1 for values of less than about 70. The
DAB ρ L
(c − c A 0 )
ordinate is A , where cA is the exit concentration, cA0 inlet concentration, and cAi
(c Ai − c A0 )
concentration at the interface between the wall and the gas. The dimensionless abscissa is
W ⎛ D⎞ ⎛π⎞
or N Re N Sc ⎜ ⎟ ⎜ ⎟ , where W is flow in kg/s and L is length of mass-transfer
DAB ρ L ⎝ L ⎠ ⎝4⎠
section in m.
Since the experimental data follow the rodlike plot, that line should be used. The velocity
profile is assumed fully developed to parabolic form at the entrance.
For liquids that have small values of DAB, data follow the parabolic flow line, which is as
W
follows for over 400.
DAB ρ L

2
−
c A − c A0 ⎛ W ⎞ 3
= 5.5 ⎜ ⎟ . . . (12.3)
c Ai − c A0 ⎝ D AB ρ L ⎠
26
 1 Molecular and
Graetz Turbulent Diffusion
Parabolic

10
-1 Rodlike
flow
Parabolic
flow
C A - C A0
-2
10
C Ai - C A0

-3
10 Approximate
Leveque Equation

-4
10
1 10 10
2
10
3 4
10
5
10
6
10
7
10

W D π
Or NRe NSe
D AB ρL L 4

Figure 12.1 : Data for Diffusion in a Fluid in Streamlined Flow Inside a Pipe : Filled Circles,
Vaporization Data of Gilliland and Sherwood, Open Circles, Dissolving Solid Data of Linton and
Sherwood ( Ref. Chemical Engg Progr. 46, 258, 1950)

12.2.2 Mass Transfer for Turbulent Flow Inside Pipes

Dvρ
For turbulent flow for Re = above 2100 for gases or liquids flowing inside a pipe,
μ
0.83 0.33
D k p D ⎛ Dvρ ⎞ ⎛ μ ⎞
Sh = kc′ = c BM = 0.023 ⎜ ⎟ ⎜ ⎟ . . . (12.4)
DAB P DAB ⎝ μ ⎠ ⎝ ρ DAB ⎠
The equation holds for Sc = 0.6 to 3000. Note that the Sc for gases is in the range 0.5-3
and for liquids is above 100 in general. Eq. (12.4) for mass transfer and Eq. (8.254) for
heat transfer inside a pipe are similar to each other.

12.3 LAMINAR FLOW AND BOUNDARY-LAYER THEORY

IN MASS TRANSFER
In Figure 12.2 the concentration boundary layer is shown where the concentration of the
fluid approaching the plate is cA∞ and cAS in the fluid adjacent to the surface.
We start by using the differential mass balance, and simplifying it for steady state where
∂c A
= 0, RA = 0 , flow only in the x and y directions, so vx = 0, and neglecting diffusion
∂t
in the x and z directions to give

∂c A ∂c ∂ 2cA
vx + v y A = DAB . . . (12.5)
∂x ∂y ∂y 2
The momentum boundary-layer equation is very similar.

∂vx ∂v μ ∂ 2 vx
vx + vy x = . . . (12.6)
∂x ∂y ρ ∂y 2

The thermal boundary-layer equation is also similar.

∂T ∂T k ∂ 2T
vx + vy = . . . (12.7)
∂x ∂y ρc p ∂y 2
27
Mass Transfer c A∞

y Edge of
concentration
cA
δc boundary layer

c AS

X=0 x
Figure 12.2 : Concentration Boundary Layer

The continuity equation used previously is

∂vx ∂v y
+ =0
∂x ∂y

The dimensionless concentration boundary conditions are

vx T − TS c − c AS
= = A =0 . . . (12.9)
v∞ T∞ − TS c A∞ − c AS

at y = 0

vx T − TS c − c AS
= = A =1 . . . (12.10)
v∞ T∞ − TS c A∞ − c AS

at y = ∞

The velocity gradient at the surface is

1
⎛ ∂vx ⎞ v
⎜ ⎟ = 0.332 ∞ Re x2 . . . (12.11)
⎝ ∂y ⎠ y = 0 x

x v∞ ρ
where Re x =
μ

vx c − c AS
= A . . . (12.12)
v∞ c A∞ − c AS

Differentiating Eq. (12.12) and combining the result with Eq. (8.25),

⎛ ∂c A ⎞ ⎛ 0.332 1 ⎞

⎜ ⎟ = (c A∞ − c AS ) ⎜ Re x2 ⎟ . . . (12.13)
⎝ ∂y ⎠y = 0 ⎜ x ⎟
⎝ ⎠
The convective mass-transfer equation can be written as follows and also related with
Fick’s equation for dilute solutions:

⎛ ∂c ⎞
N Ay = kc′ (c AS − c A∞ ) = − DAD ⎜ A ⎟ . . . (12.14)
⎝ ∂y ⎠ y = 0

Combining Eqs. (12.13) and (12.14),

1
kc′ x
= Shx = 0.332 Re x2 . . . (12.15)
DAB

The relationship is restricted to gases with a Sc = 1.0.

28
The relationship between the thickness δ of the hydrodynamic and δc of the concentration Molecular and
Turbulent Diffusion
boundary layers where the Schmidt number is not 1.0 is
1
δ
= Sc 3 . . . (12.16)
δc
As a result, the equation for the local convective mass-transfer coefficient is
1 1
kc′ x
= Shx = 0.332 Re x2 Sc 3 . . . (12.17)
DAB

We can obtain the equation for the mean mass-transfer coefficient kc′ from x = 0 to x = L
for a plate of width b by integrating as follows :
b L
kc′ =
bL ∫0 kc′ dx . . . (12.18)

The result is
1 1
kc′ L
= Sh = 0.664 Re L2 Sc 3 . . . (12.19)
DAB
This is similar to the heat-transfer equation for a flat plate and also checks the
experimental mass-transfer equation for a flat plate.
SAQ 1
(a) What is the major difference between laminar and turbulent mass transfer?
(b) Show that for a mass transfer in a boundary layer over a flat plate
1 1
Sh = 0.664 Re L2 Sc 3

12.4 PRANDTL MIXING LENGTH AND TURBULENT EDDY

MASS DIFFUSIVITY
In many applications the flow in mass transfer is turbulent and not laminar. The turbulent
flow of a fluid is quite complex and the fluid undergoes a series of random eddy
movements throughout the turbulent core. When mass transfer is occurring, we refer to
this as eddy mass diffusion. In unit 8, we derived equations for turbulent eddy thermal
diffusivity and momentum diffusivity using the Prandtl mixing length theory.
In a similar manner we can derive a relation for the turbulent eddy mass diffusivity, εM.
Eddies are transported a distance L, called the Prandtl mixing length, in the y direction.
At this point L the fluid eddy differs in velocity from the adjacent fluid by the velocity
v′x , which is the fluctuating velocity component. The instantaneous rate of mass transfer
of A at a velocity v′y for a distance L in the y direction is

J ∗Ay = c′A v′y . . . (12.20)

where c ′A is the instantaneous fluctuating concentration. The instantaneous concentration

of the fluid is c A = c′A + c where c A is the mean value and c ′A the deviation from the
mean value. The mixing length L is small enough so the concentration difference is 29
Mass Transfer dc A
c′A = L . . . (12.21)
dy

The rate of mass transported per unit area is J ∗Ay . Combining Eqs. (12.20) and (12.21),

dc A
J ∗Ay = − v′y L . . . (12.22)
dy

From Eq. (5.7-23),

dv x
v′y = v′x = L . . . (12.23)
dy

Substituting Eq. (12.23) into Eq. (12.22),

dv x dc A
J ∗Ay = − L2 . . . (12.24)
dy dy

dv x
The term L2 is called the turbulent eddy mass diffusivity εM. Combining
dy
Eq. (12.24) with the diffusion equation in terms of DAB, the total flux is

dc A
J ∗Ay = − ( D AB + ε M ) . . . (12.25)
dy

In Mass Transfer from Turbulent Boundary Layer Flow Over a Flat Plate
2
kx
jM = Sc 3 = 0.0296 Re0.2
x . . . (12.26)
V

For 5 × 105 < Re x < 107

Nu x Shx k x ν D kx
Since St x = = = x = . . . (12.27)
Re x Pr Re x Sc D Vx ν V

where kx is the local mass transfer coefficient.

For average values in case of a flat plate, the j factors are analogous to the skin
friction coefficient as given below
Laminar
Cf 0.664
j H = jM = = 1
. . . (12.28)
2
(Re L )2

Turbulent
Cf 0.037
j H = jM = = . . . (12.29)
2 (Re L )0.2

When heat and mass transfer take place simultaneously, the ratio of hx and kx can
be of interest. Both for laminar and turbulent boundary flows,
2 2
hx ⎛ Sc ⎞ 3
= ρ c p ⎜ ⎟ = ρ c p Le 3 . . . (12.30)
kx ⎝ Pr ⎠
30
 where the Lewis number is defined as Molecular and
Turbulent Diffusion
Sc α
Le = = . . . (12.31)
Pr D
The same relation is also applicable for the average values of the heat and mass
transfer coefficients, namely
2 2
hm ⎛ α ⎞3
= ρ c p ⎜ ⎟ = ρ c p Le 3 . . . (12.32)
km ⎝D⎠
SAQ 2
(a) What is Prandtl mixing length theory?
(b) What is the significance of Lewis number?
(c) Define turbulent eddy mass diffusivity.

12.5 DIFFUSION IN A LAMINAR FALLING FILM

Consider mass transfer of solute A into a laminar falling film. Such problems are
important in wetted-wall columns, in developing theories to explain mass transfer in
stagnant pockets of fluid, and in turbulent mass transfer. The solute A in the gas is
observed at the interface and then diffuses a distance into the liquid so that it has not
penetrated the whole distance x = δ at the wall. At steady state the inlet concentration
cA = 0. At a point z distance from the inlet the concentration profile of cA is shown in
Figure 12.3.

gas x

NAX z liquid

Velocity NAz z
Profile

L uz (x) Δx

NAx x + Δx
NAx x
Δz
cA vs. x
cA o cA L

Unit
0
Width
NAz z + Δz
δ
(a) (b)
Figure 12.3 : Diffusion of a Solute A in a Laminar Film (a) Velocity Profile and Concentration Profile,
(b) Small Element for Mass Balance

A mass balance will be made on the element shown in Figure 12.3(b). For steady state,
rate of input = rate of output.
N Ax (1Δz ) + N Az (1Δx) = N Ax (1Δz ) + N Az (1Δx) . . . (12.33)
x z x + Δx z + Δz 31
Mass Transfer For a dilute solution the diffusion equation for A in the x direction is
∂c A
N Ax = − DAB + zero convection . . . (12.34)
∂x
For the z direction the diffusion is negligible.
N Az = 0 + c A v z . . . (12.35)
Dividing Eq. (12.33) by Δx Δz, letting Δx and Δz approach zero, and substituting
Eqs. (12.34) and (12.35) into the result, we obtain
∂c A ∂ 2cA
vz = DAB . . . (12.36)
∂z ∂x 2
that the velocity profile is parabolic and is
⎡ ⎛ x ⎞2 ⎤
vz = vz max ⎢1 − ⎜ ⎟ ⎥
⎢⎣ ⎝ δ ⎠ ⎥⎦

⎛3⎞
and vz max = ⎜ ⎟ vz a v
⎝2⎠
If the solute has penetrated only a short distance into the fluid, i.e. short contact times of t
z
seconds equals , then the A that has been carried along at the velocity vmax or vmax if
vmax
the subscript z is dropped. Then Eq. (12.36) becomes
∂c A ∂ 2c A
= DAB . . . (12.37)
⎛ z ⎞ ∂x 2
∂⎜ ⎟
⎝ vmax ⎠
Using the boundary conditions of cA = 0 at z = 0, cA = CAD at x = 0, and cA = 0 at x = ∞ we
can integrating Eq. (12.37) to obtain
⎛ ⎞
⎜ ⎟
= er f c ⎜ ⎟
cA x
. . . (12.38)
c A0 ⎜ z ⎟
⎜⎜ 4 DAB ⎟⎟
⎝ vmax ⎠
where erf y is the error function and erfc y = 1 − erf y . Values of erf y are standard
tabulated functions (Annexure I).
To determine the local molar flux at the surface x = 0 at position z from the top entrance,
we write
∂c A DAB vmax
N Ax ( z ) x=0
= − DAB = c A0 . . . (12.39)
∂x x=0 πz
The total moles of A transferred per second to the liquid over the entire length z = 0 to
z = L, where the vertical surface is unit width is
L ⎛ ⎞
N A ( L . 1) = (1) ∫ ⎜ N Ax
⎜
⎟ dz
=0⎟
. . . (12.40)
0 ⎝ x ⎠
1
L ⎛ DAB vmax ⎞ 2 1
= (1) ∫0 c A0 ⎜
⎝ π ⎟
⎠ 1
dz
z2
4 DAB vmax
= ( L . 1) c A0
πL

32
 L Molecular and
The term is tL, time of exposure of the liquid to the solute A in the gas. This means Turbulent Diffusion
vmax
0.5 1
the rate of mass transfer is proportional to DAB and . This is the basis for the
t L0.5
penetration theory in turbulent mass transfer where pockets of liquid are exposed to
unsteady-state diffusion (penetration) for short contact times.

12.6 MASS TRANSFER FOR FLOW OUTSIDE SOLID

SURFACES
12.6.1 Mass Transfer in Flow Parallel to Flat Plates
The mass transfer and vaporization of liquids from a plate or flat surface to a flowing
stream is of interest in the drying of inorganic and biological materials, in evaporation of
solvents from paints, for plates in wind tunnels, and in flow channels in chemical process
equipment.
When the fluid flows past a plate in a free stream in an open space the boundary layer is
not fully developed. For gases or evaporation of liquids in the gas phase and for the
Lvρ
laminar region of Re L = less than 15000, the data can be represented within
μ
± 25% by the equation

J D = 0.664 Re−L 0.5 . . . (12.41)

Writing Eq. (12.41) in terms of Sherwood number Sh,

1
kc′ L
= Sh = 0.664 Re0.5
L Sc
3 . . . (12.42)
DAB

where L is the length of the plate in the direction of flow. For this geometry
f
J D = J H = . For gases with ReL = 15000 – 300000, the data are represented within
2
f
± 30% by J D = J H = as
2

J D = 0.036 Re−L 0.2 . . . (12.43)

Experimental data for liquids are correlated within about ± 40% by the following for
ReL = 600 – 50000

J D = 0.99 Re−L 0.5 . . . (12.44)

12.6.2 Mass Transfer for Flow Past Single Spheres

D p vρ
For flow past single spheres and for very low Re = , where v is the average
μ
kc′ D p
velocity in the empty test section before the sphere, the Sherwood number ( Sh = ),
DAB
should approach a value of 2.0. This can be shown as
2 DAB
NA = (c A1 − c A2 ) = kc (c A1 − c A2 ) . . . (12.45)
Dp

where Dp is the diameter of the sphere.

33
Mass Transfer The mass-transfer coefficient kc, which is kc′ for a dilute solution, is then
2 D AB
kc′ = . . . (12.46)
Dp

kc′ D p
Rearranging, = Sh = 2.0 . . . (12.47)
DAB

Of course, natural convection effects could increase kc′ .

Correlation for the may be presented with the following modified equation
1
Sh = 2 + 0.552 Re 0.53
Sc 3 . . . (12.48)
This equation also holds for heat transfer where the Prandtl number replaces the Schmidt
hD p
number and the Nusselt number replaces the Sherwood number. Eq. (12.48) holds
k
good for Schmidt number range of 0.6-2.7 and Reynolds number range of 1 – 48000.
For liquids, with Reynolds number range of 2 to about 2000, the following can be used.
1
Sh = 2 + 0.95 Re0.50 Sc 3 . . . (12.49)
For liquids, with Reynolds number of 2000 – 17000, the following can be used.
1
Sh = 0.347 Re0.62 Sc 3 . . . (12.50)

12.7 MASS TRANSFER TO PACKED BEDS

Mass transfer to and from packed beds occurs often in processing operations, including
drying operations, adsorption or desorption of gases or liquids by solid particles such as
charcoal, and mass transfer of gases and liquids to catalyst particles. Using a packed bed
a large amount of mass-transfer area can be contained in a relatively small volume.
The void fraction ε (m3) in a bed is volume of the void space divided by the total volume
of void space plus solid. The values range from ε = 0.3 – 0.5 in general. Because of flow
channeling, nonuniform packing, etc., accurate experimental data are difficult to obtain
and data from different investigators can deviate considerably.
In case of gases, for a Reynolds number range of 10-10000, the following equation is
recommended
0.4548 − 0.4069
JD = JH = Re . . . (12.51)
ε
The above Eq. (12.51) indicates an average deviation of about ± 20% and a maximum of
about ± 50%.
It has been shown that JD and JH are approximately equal. The Reynolds number is
D p v′ ρ
defined as Re = , where Dp is diameter of the spheres and v′ is the superficial
μ
mass average velocity in the empty tube without packing. For a Reynolds number
D p v′ ρ
range of 0.0016 – 55 and a Schmidt number range of 165 – 70 600, the equation
μ
to use is
2
1.09 −
JD = Re 3 . . . (12.52)
ε
34
For liquid with Reynolds number range of 55 – 1500 and a Schmidt number range of Molecular and
165 – 10690, Turbulent Diffusion

0.250 − 0.31
JD = N Re . . . (12.53)
ε
or, as an alternate, Eq. (12.51) can be used for liquids for a Reynolds number range of
10 – 1500.
For fluidized beds of spheres, Eq. (12.51) can be used for gases and liquids and a
Reynolds number range of 10 4000. For liquids in a fluidized bed and a Reynolds
number range of 1 to 10,

J D = 1.1068 Re − 0.72 . . . (12.54)

If packed beds of solids other than spheres are used, approximate correlation factors can
be used with Eqs. (12.51)-(12.53) for spheres. This is done, for example, for a given
nonspherical particle as follows. The particle diameter to use in the equations to predict
JD is the diameter of a sphere with the same surface area as the given solid particle. The
flux to these particles in the bed is then calculated using the area of the given particles.
12.7.1 Calculation Method for Packed Beds
To calculate the total flux in a packed bed, JD first obtained and then kc in m/s from the
Jn. Then knowing the total volume Vb m3 of the bed (void plus solids), the total external
surface area A m2 of the solids for mass transfer is calculated using the following :
6 (1 − ε)
a= . . . (12.55)
Dp

A = a Vb . . . (12.56)
where a is the surface area (m2)/total volume (m3) of bed when the solids are spheres.
To calculate the mass-transfer rate the log mean driving force at the inlet and outlet of the
bed should be used.
(c Ai − c A1 ) − (c Ai − c A2 )
N A A = Akc . . . (12.57)
c − c A1
ln Ai
c Ai − c A2
where the final term is the log mean driving force : cAi is the concentration at the surface
of the solid, in kg mol/m3; cA1 is the inlet bulk fluid concentration; and cA2 is the outlet.
The material-balance equation on the bulk stream is
N A A = V (c A2 − c A1 ) . . . (12.58)
where V is volumetric flow rate of fluid entering in m3/s. Eqs. (12.57) and (12.58) must
both be satisfied. The use of these two equations is similar to the use of the log mean
temperature difference and heat balance in heat exchangers. These two equations can also
be used for a fluid flowing in a pipe or past a flat plate, where A is the pipe wall area or
plate area.
SAQ 3
(a) Define voidage.
(b) How does mass transfer occur in a packed bed?
(c) What is a fluidized bed?

35
Mass Transfer
12.8 MASS TRANSFER FOR FLOW PAST SINGLE
CYLINDERS
Experimental data have been obtained for mass transfer from single cylinders when the
flow is perpendicular to the cylinder. The cylinders are long and mass transfer to the ends
of the cylinder is not considered.
For the Schmidt number range of 0.6 to 2.6 for gases and 1000 to 3000 for liquids and a
Reynolds number range 50 to 50 000 the correlation to use is as follows

J D = 0.600 (Re) − 0.487 . . . (12.59)

This correlation can also be used for heat transfer with JD = JH.

12.9 LIQUID METALS MASS TRANSFER

In recent years several correlations for mass-transfer coefficients of liquid metals have
appeared in the literature. It has been found that with moderate safety factors, the
correlations for non-liquid metals mass transfer may be used for liquid metals mass
transfer. Care must be taken to ensure that the solid surface is wetted. Also, if the solid is
an alloy, there may exist a resistance to diffusion in the solid phase.

12.10 MASS TRANSFER TO SUSPENSIONS OF SMALL

PARTICLES
Mass transfer from or to small suspended particles in an agitated solution occurs in a
number of process applications such as liquid phase hydrogenation, hydrogen diffuses
from gas bubbles, through an organic liquid, and diffusion to small suspended catalyst
particles. Some more examples are : fermentations, oxygen diffusion from small gas
bubbles, through the aqueous medium, diffusion to small suspended microorganisms, etc.
For a liquid-solid dispersion, increased agitation over and above that necessary to freely
suspended very small particles has very little effect on the mass transfer coefficient kL to
the particles. When the particles in a mixing vessel are just completely suspended,
turbulence forces balance those due to gravity, and the mass-transfer rates are the same as
for particles freely moving under gravity. With very small particles of say a few μ m or
so, which is the size of many microorganisms in fermentations and some catalyst
particles, their size is smaller than eddies, which are about 100 μ m or so in size. Hence,
increased agitation will have little effect on mass transfer except at very high agitation.
For a gas-liquid-solid dispersion, such as in fermentation, the same principles hold.
However, increased agitation increases the number of gas bubbles and hence the
interfacial area. The mass-transfer coefficients from the gas bubbles to the liquid and
from the liquid to the solid are relatively unaffected.
12.10.1 Mass Transfer to Small Particles < 0.6 mm
Equations to predict mass transfer to small particles in suspension have been developed
which cover three size ranges of particles. The following equation for particles < 0.6 mm
(600 μm) is discussed first.
The following equation (Eq. (12.60)) has been shown to hold to predict mass-transfer
coefficients from small gas bubbles such as oxygen or air to the liquid phase or from the
liquid phase to the surface of small catalyst particles, microorganisms other solids, or
liquid drops.
1
2 DAB −
2
⎛ Δ ρμc g ⎞ 3
k L′ = + 0.31 Sc 3 ⎜⎜ ⎟⎟ . . . (12.60)
⎝ ρc ⎠
Dp 2
36
where DAB is the diffusivity of the solute A in solution in m2/s, Dp is the diameter of the Molecular and
gas bubble or the solid particles in m, μ c is the viscosity of the solution in kg/m ⋅ s,
Turbulent Diffusion

g = 9.80665 m/s2, Δρ = (ρc − ρ p ) or (ρ p − ρc ) , ρc is the density of the continuous

phase in kg/m3, and ρp is the density of the gas or solid particle. The value of Δρ is
always positive.
The first term on the right in Eq. (12.60) is the molecular diffusion term, and the second
term is that due to free fall or rise of the sphere by gravitational forces. This equation has
been experimentally checked for dispersions of low-density solids in agitated dispersions
and for small gas bubbles in agitated systems.
Eq. (12.60) has also been shown to apply to heat transfer and can be written as follows :
1
hD p 1 ⎛ D 3p ρc Δρ g ⎞ 3
Nu = = 2.0 + 0.31 Pr 3 ⎜ ⎟ . . . (12.61)
k ⎜ μ 2 ⎟
⎝ c ⎠
12.10.2 Mass Transfer to Large Gas Bubbles > 2.5 mm
For large gas bubbles or liquid drops > 2.5 mm, the mass-transfer coefficients can be
predicted by
1
⎛ Δ ρμc g ⎞ 3
k L′ = 0.42 Sc − 0.5 ⎜⎜ ⎟⎟ . . . (12.62)
⎝ ρc ⎠
2

Large gas bubbles are produced when pure liquids are aerated in mixing vessels and
sieve-plate columns. In this case the mass-transfer coefficient k L′ or kL is independent of
the bubble size and is constant for a given set of physical properties. For the same
physical properties the large bubble Eq. (7.43) gives values of kL about three to four
times larger than Eq. (7.41) for small particles. Again, Eq. (7.43) shows that the kL is
essentially independent of agitation intensity in an agitated vessel and gas velocity in a
sieve-tray tower.
12.10.3 Mass Transfer to Particles in Transition Region
In mass transfer in the transition region between small and large bubbles in the size range
0.6 to 2.5 mm, the mass-transfer coefficient can be approximated by assuming that it
increases linearly with bubble diameter.
12.10.4 Mass Transfer to Particles in Highly Turbulent Mixers
In the preceding three regions, the density difference between phases is sufficiently large
to cause the force of gravity to primarily determine the mass transfer coefficient. This
also includes solids just completely suspended in mixing vessels. When agitation power
is increased beyond that needed for suspension of solid or liquid particles and the
turbulence forces become larger than the gravitational forces. Eq. (12.60) is not followed
and the following equation should be used where small increases in k L′ are observed.
1
2
⎛ ( PV ) μc ⎞4
k L′ Sc 3 = 0.13 ⎜ ⎟⎟ . . . (12.63)
⎜ ρ2
⎝ c ⎠
where PV is power input per unit volume. The data deviate substantially by up to 60%
from the correlation. In the case of gas liquid dispersions it is quite impractical to exceed
gravitational forces by agitation systems.
Example 12.1
A tube is coated on the inside with naphthalene and has an inside diameter of
20 mm and a length of 1.10 m. Air at 318 K and an average pressure of 101.3 kPa
flows through this pipe at a velocity of 0.80 m/s. Assuming that the absolute
pressure remains essentially constant, calculate the concentration of nepthalene in
the exit air. Use the physical properties given below : 37
Mass Transfer
DAB = 6.92 × 10− 6 m 2 /s
Vapor pressure p Ai = 74.0 Pa

μair = 1.932 × 10− 5 Pa

ρair = 1.114 kg/m3

Solution
p Ai 74.0
c Ai = = = 2.799 × 10− 5 kg mol/m3.
RT (8314.3 × 318)
The Schmidt number is
π 1.932 × 10− 5
Sc = = = 2.506
ρ DAB 1.114 × 6.92 × 10− 6

The Reynolds number is

D v ρ 0.020 (0.80) (1.114)
Re = = = 922.6
π 1.932 × 10− 5
Hence, the flow is laminar. Then,
D π 0.020 π
Re . Sc . = 922.6 (2.506) = 33.02
L 4 1.10 4
Using Figure 12.1 and the rodlike flow line,
(c A − c A0 )
= 0.55
(c Ai − c A0 )

Also, c A0 (inlet) = 0,

(c A − 0)
Then, = 0.55 .
(2.799 × 10− 5 − 0)

Solving, cA (exit concentration) = 1.539 × 10− 5 kg mol/m3 .

Example 12.2
A large volume of pure water at 26.1oC is flowing parallel to a flat plate of solid
benzoic acid, where L = 0.224 m in the direction of flow. The water velocity is
0.061 m/s. The solubility of benzoic acid in water is 0.02948 kg mol/m3. The
diffusivity of benzoic acid is 1.245 × 10− 9 m 2 /s . Calculate the mass transfer
coefficient kL and the flux NA.
Solution
Since the solution is quite dilute, the physical properties of water at 26.1oC can be
used as given below :

μ = 8.71 × 10− 4 Pa ⋅ s

ρ = 996 kg/m 3

DAB = 1.245 × 10− 9 m 2 /s

The Schmidt number is
8.71 × 10− 4
Sc = = 702
996 (1.245 × 10− 9 )
38
 The Reynolds number is Molecular and
Turbulent Diffusion
L v ρ 0.244 (0.0610) (996)
Re L = = −4
= 1.700 × 104
μ 8.71 × 10

Using Eq. (12.44),

J D = 0.99 Re−L 0.5 = 0.99 (1.700 × 104 )− 0.5 = 0.00758

The definition of JD is
2
k′
JD = c ( Sc ) 3
v
2
−
Solving for kc′ , kc′ = J D v ( Sc) 3 . Substituting known values and solving,
2
−
kc′ = 0.00758 (0.0610) (702) 3 = 5.85 × 10− 6 m/s

In this case, diffusion is for A through non-diffusing B, so kc is obtained from

kc′
NA = (c A1 − c A2 ) = kc (c A1 − c A2 )
xBM

Since the solution is very dilute, xBM ≅ 1.0 and kc′ ≅ kc . Also,
c A1 = 2.948 × 10− 2 kg mol/ m 3 (solubility) and cA2 = 0 (large volume of fresh
water). Substituting into above equation,

N A = (5.85 × 10− 6 ) (0.02948 − 0) = 1.726 × 10− 7 kg mol/s.m2

Example 12.3
Calculate the value of the mass-transfer coefficient and the flux for mass transfer
from a sphere of naphthalene to air at 45o@ and 1 atm abs flowing at a velocity of
0.305 m/s. The diameter of the sphere is 25.4 mm. The diffusivity of naphthalene
in air at 45o@ is 6.92 × 10− 6 m 2 /s and the vapour pressure of solid naphthalene is
0.555 mm Hg. Use English and SI units.
Solution

In English units D AB = 6.92 × 10 − 6 (3.875 × 10 4 ) = 0.2682 ft 2 /h . The diameter

D p = 0.0254 m = 0.0254 (3.2808) = 0.0833 ft . The physical properties of air will
be used since the concentration of naphthalene is low.

μ = 1.93 × 10− 5 Pa.s = 1.93 × 10− 5 (2.4191 × 103 ) = 0.0467 lb m /ft.h

1.113
ρ = 1.113 kg/m3 = = 0.0695 lb m /ft 3 1bm / ft 3
16.0185
v = 0.305 m/s = 0.305 (3600 × 3.2808) = 3600 ft/h

The Schmidt number is

μ 0.0467
Sc = = = 2.505
ρ DAB 0.0695 (0.2682)

1.93 × 10− 5
Sc = = 2.505
1.113 (6.92 × 10− 6 ) 39
Mass Transfer The Reynolds number is
Dp v ρ 0.0833 (3600) (0.0695)
Re = = = 446
μ 0.0467
0.0254 (0.3048) (1.113)
Re = = 446
1.93 × 10− 5

For gases,
1 1
Sh = 2 + 0.552 (Re)0.53 ( Sc) 3 = 2 + 0.552 (446)0.53 (2.505) 3 = 21.0

L Dp
Now, Sh = kc′ = kc′
DAB DAB

Substituting the knowns and solving,

kc′ (0.0822)
21.0 = kc′ = 67.6 ft/h
0.2682
kc′ (0.0254)
21.0 = −6
kc′ = 5.72 × 10− 3 m/s
6.92 × 10

RT
Again, kc′ c = kc′ = kG′ P
P

Hence, for T = 45 + 273 = 318 K = 318 (1.8) = 574o R ,

kc′ 67.6
kG′ = = = 0.1616 lb mol/h.ft 2 .atm
RT (0.730) (573)

5.72 × 10− 3
kG′ = = 2.163 × 10− 9 kg mol/s.m 2 .Pa
8314 (318)

Since the gas is very dilute, y BM ≅ 1.0 and kG′ ≅ kG . Substituting into the
following equation for A diffusing through stagnant B and noting that
0.555
p A1 = = 7.303 × 10− 4 atm = 74.0 Pa and p A 2 = 0 (pure air),
760

N A = kG ( p A1 − p A2 ) = 0.1616 (7.303 × 10− 4 − 0)

= 1.180 × 10− 4 lb mol/h.ft 2 F

= 2.163 × 10− 9 (74.0 − 0) = 1.599 × 10− 7 kg mol/s.m 2

The area of the sphere is

A = π D 2p = π (0.0833) 2 = 2.18 × 10− 2 ft 2

2
⎛ 1 ⎞
−2 −3
= (2.18 × 10 ) ⎜ ⎟ = 2.025 × 10 m
2
⎝ 3.2808 ⎠
Total amount evaporated

= N A A = (1.18 × 10− 4 ) (2.18 × 10 − 2 ) = 2.572 × 10− 6 lb mol/h ×10 −6

= (1.599 × 10− 7 ) (2.025 × 10− 3 ) = 3.238 × 10−10 kg mol/s

40
Example 12.4 Molecular and
Turbulent Diffusion
Calculate the maximum rate of absorption of O2 in a fermenter from air bubbles at
1 atm abs pressure having diameters of 100 μ m at 37oC into water having a zero
concentration of dissolved O2. The solubility of O2 from air in water at 37oC is
2.26 × 10− 7 g mol O2/m3 liquid or 2.26 × 10− 4 kg mol O2/m3. The diffusivity of O2
in water at 37oC is 3.25 × 10− 9 m2/s. Agitation is used to produce the air bubbles.

Solution

The mass-transfer resistance inside the gas bubble to the outside interface of the
bubble can be neglected since it is negligible. Hence, the mass-transfer coefficient
k L′ outside the bubble is needed. The given data are

D p = 100 μ m = 1 × 10− 4 m

D AB = 3.25 × 10− 9 m 2 /s

At 37oC,

μc (water) = 6.947 × 10− 4 Pa .s = 6.947 × 10− 4 kg/m.s

ρc (water) = 994 kg/m3

ρc (air) = 1.13 kg/m3

μc 6.947 × 10− 4
Sc = = = 215
ρc DAB (994) (3.25 × 10− 9 )

2 2
Sc 3 = (215) 3 = 35.9

Δρ = ρc − ρ p = 994 − 1.13 = 993 kg/m3

Substituting in the equation,

1
⎛ Δ ρμ c g ⎞ 3
2
2 DAB −
k L′ = + 0.31 N Sc3 ⎜⎜ ⎟⎟
⎝ ρc ⎠
Dp 2

1
2 (3.25 × 10 ) 0.31 ⎡ 993 × 6.947 × 10− 4 × 9.806 ⎤ 3
−9
= + ⎢ ⎥
1 × 10− 4 35.9 ⎢⎣ (994) 2 ⎥⎦

= 6.50 × 10− 5 + 16.40 × 10− 5 = 2.290 × 10 − 4 m/s

The flux is as follows assuming k L = k L′ for dilute solutions.

N A = k L (c A1 − c A 2 ) = 2.290 × 10− 4 (2.26 × 10 − 4 − 0)

= 5.18 × 10− 8 kg mol O 2 /s.m 2

Knowing the total number of bubbles and their area, the maximum possible rate of
transfer of O2 to the fermentation liquid can be calculated.
41
Mass Transfer
12.11 SUMMARY
Present unit is devoted to discuss mass transfer phenomena in laminar and turbulent flow.
Laminar mass transport in tubes and over a flat plates are discussed. Prandtl mixing
length theory is described to give more insight of turbulent mass transfer. Mass transfer
for flow outside a solid surface, flow parallel to flat plates and flow past single spheres
are discussed. One advanced area of research is the mass transfer in packed bed. Particle
with small dimensions and gas bubbles with large dimension are affected by mass
transfer. These phenomena are discussed in the present unit. You will appreciate that
mass transfer is alike to the convective heat transfer phenomena for this study.

12.12 KEY WORDS

Laminar Mass Transfer : Streamlined mass transfer.
Turbulent Mass Transfer : Mixing of masses along the direction
perpendicular to flow.
Packed Bed : A large amount of mass transfer area can be
contained in a relatively small volume.
Concentration Boundary Layer : A boundary layer alike to that of convective
boundary layer arising due to concentration
difference.
Fluidized Bed : Fluid like behaviour of solid particles (may be
gas-liquid or solid-gas combination).

12.13 ANSWER TO SAQS

Refer the preceding text for all the Answers to SAQs.

42
 Molecular and
REFERENCES Turbulent Diffusion

F. P. Incropera and D. P. Dewitt (2004), Fundamentals of Heat and Mass Transfer,

5th Edition, John Wiley and Sons.
W. M. Rohsenow and H. C. Choi (1961), Heat Mass and Momentum Transfer,
Prentice-Hall Englewood Cliffs, N. J.
E. R. G. Eckert and R. M. Drake Jr. (1959), Heat and Mass Transfer, McGraw-Hill,
New York.
P. K. Nag (2002), Heat Transfer, Tata McGraw-Hill Publishing Company Limited,
New Delhi.
C. J. Geankoplis (2004), Transport Processes and Unit Operations, 3rd Edition, Prentice-
Hall of India Pvt. Ltd, New Delhi.
R. B. Bird, W. E. Stewart, and E. N. Lightfoot (1960), Transport Phenomena, Wiley,
New York.

43