Mass Transfer Third Year Dr.

ARKAN JASIM HADI

Mass transfer theories

1. The Two-Film Theory

The two-film theory of Whitman (1923) was the first serious attempt to represent
conditions occurring when material is transferred in a steady state process from one fluid
stream to another. In this approach, it is assumed that a laminar layer exists in each of the two
fluids. Outside the laminar layer, turbulent eddies supplement the action caused by the
random movement of the molecules, and the resistance to transfer becomes progressively
smaller as shown in Figure below. The thicknesses of the two films are z1 and z2 . Equilibrium
is assumed to exist at the interface and therefore the relative positions of the points C and D
are determined by the equilibrium relation between the phases.

interface

The rate of mass transfer per unit area in terms of the two-film theory for equimolecular
counterdiffusion is given for the first phase as:

=−

∗
( − )
=
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Mass Transfer Third Year Dr. ARKAN JASIM HADI

In the form of partial pressure:

∗
( − )
=

∗ ∗
( − ) ( − )
= =

Where: Z = Zg + ZL

The rate of mass transfer per unit area from the gas film:

( )
= ( − )
.

The rate of mass transfer per unit area from the liquid film:

( )
= ( − )

The relation between the partial pressure (PA) and concentration (CA):

Raoult's law:

Henry's law:

Where: H is the Henry's constant.

∗ ∗
= or =
∗ ∗
= or =

= or =

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

2. The Penetration Theory

The penetration theory was suggested in 1935 by Higbie who was investigating
whether or not a resistance to transfer existed at the interface when a pure gas was absorbed in
a liquid. In his experiments, a slug-like bubble of carbon dioxide was allowed rise through a
vertical column of water in a 3 mm diameter glass tube. As the bubble rose, the displaced
liquid ran back as a thin film between the bubble and the tube, Higbie assumed that each
element of surface in this liquid was exposed to the gas for the time taken for the gas
bubble to pass it; that is for the time given by the quotient of the bubble length and its
velocity. It was further supposed that during this short period, which varied between 0.01 and
0.1 s in the experiments, absorption took place as the result of unsteady state molecular
diffusion into the liquid, and, for the purposes of calculation, the liquid was regarded as
infinite in depth because the time of exposure was so short.

The way in which the concentration gradient builds up as a result of exposing a liquid -
initially pure - to the action of a soluble gas is shown in Figure 10.6. The percentage
saturation of the liquid is plotted agains the distance from the surface for a number of
exposure times in arbitrary units. Initially only the surface layer contains solute and the
concentration changes abruptly from 100 percent to 0 percent at the surface. For progressively
longer exposure times the concentration profile develops as shown, until after an infinite time
the whole of the liquid becomes saturated. The shape of the profiles is such that at any time
the effective depth of liquid which contains an appreciable concentration of solute can be
specified. If this depth of penetration is less than the total depth of liquid, no significant error
is introduced by assuming that the total depth is infinite.

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

The work of Higbie laid the basis of the penetration theory in which it is assumed that
the eddies in the fluid bring an element of fluid to the interface where it is exposed to the
second phase for a definite interval of time, after which the surface element is mixed with the
bulk again. Thus, fluid whose initial composition corresponds with that of the bulk fluid
remote from the interface is suddenly exposed to the second phase. It is assumed that
equilibrium is immediately attained by the surface layers, that a process of unsteady state
molecular diffusion then occurs and that the element is remixed after a fixed interval of
time. In the calculation, the depth of the liquid element is assumed to be infinite and this is
justifiable if the time of exposure is sufficiently short for penetration to be confined to the
surface layers. Throughout, the existence of velocity gradients within the fluids is ignored and
the fluid at all depths is assumed to be moving at the same rate as the interface.

The diffusion of solute A away from the interface (y-direction) is thus given by:

The following boundary conditions apply for the pentration theory:

The mass transfer rate per unit area of surface is then given by:

Note:
film theory

n
pertration theory
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Mass Transfer Third Year Dr. ARKAN JASIM HADI

3. The Random Surface Renewal Theory

Danckwerts (1951) suggested that each element of surface would not be exposed for the
same time, but that a random distribution of ages would exist. It was assumed that the
probability of any element of surface becoming destroyed and mixed with the bulk of the fluid
was independent of the age of the element.

Thus, the overall rate of mass transfer per unit area when the surface is renewed in a random
manner is:

Where:
S is the rate of production of fresh surface per unit total area of surface.

4. The Film - Penetration Theory

A theory which incorporates some of the principles of both the two-film theory and the
penetration theory has been proposed by Toor and Marchello (1958) . The whole of the
resistance to transfer is regarded as lying within a laminar film at the interface, as in the two-
film theory, but the mass transfer is regarded as an unsteady state process. It is assumed that
fresh surface is formed at intervals from fluid which is brought from the bulk of the fluid to
the interface by the action of the eddy currents mass transfer then takes place as in the
penetration theory, except that the resistance is confined to the finite film, and material which
traverses the film is immediately completely mixed with the bulk of the fluid. For short times
of exposure, when none of the diffusing material has reached the far side of the layer, the
process is identical to that postulated in the penetration theory. For prolonged periods of
exposure when a steady concentration gradient has developed, conditions are similar to those
considered in the two-film theory.

The diffusion of solute A away from the interface (y-direction) is thus given by:

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

The following boundary conditions apply for the pentration theory:

= → =

∗
= → =

= → =

The mass transfer rate across the interface per unit area is therefore given by:

When:
Dt
is small the pentration theory applicable.
L
Dt
is large the two film theory applicable.
L

The concentration profiles near an interface on the basis of:

(a) the film theory (steady-state)
(b) the penetration-theory (unsteady-state)
(c) the film-penetration theory (unsteady-state)
are shown in Figure 10.7.

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Mass transfer coefficients

Consider the two-film theory as shown in Figure (1):

The rate of mass transfer per unit area from the gas film:

( )
= ( − )
.

The rate of mass transfer per unit area from the liquid film:

( )
= ( − )

Where:

( ) = ( )

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Since the film thickness and are difficult to define or estimate, then we rewrite the
above equations as follow:

= ( − )

= ( − )

But: and are difficult to measure, therefore we define the overall mass transfer
coefficient:

∗
= ( − )

∗
= ( − )

Where:
is the individual liquid film mass transfer coeficient.

is the individual gas film mass transfer coeficient.

is the overall mass transfer coeficient based on liquid phase.

is the overall mass transfer coeficient based on gas phase.

is the partial pressure of the gas (A) at the interface.
is the concentration of the liquid (A) at the interface.
∗
is the partial pressure of the gas phase which is in equilibrium with the liquid phase .
∗
is the concentration of the liquid phase which is in equilibrium with the gas phase .

The Relationships between the various mass transfer coefficients

= − … … … … … … … … … … … … … … . (1)

= − … … … … … … … … … … … … … … . (2)

= ( − ∗
) … … … … … … … … … … … … … … . (3)

= ( ∗
− ) … … … … … … … … … … … … … … . (4)

= + … … … … … … … … … … … … … … . (5)

= + … … … … … … … … … … … … … … . (6)

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

: Prove that = +

From Eq.(3) above:

∗
−
=

∗
− + −
=

∗
− −
= +

− −
= +

− ( − )
= +

= +

: Prove that = +

From Eq.(4) above:

∗
−
=

∗
− + −
=

∗
− −
= +

− −
= +

− −
= +

= +

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Notes:

1. The inverse to mass transfer coefficient is termed as a resistance to mass transfer.

2. The term (gas film control) refers to the resistance lie in the gas film.
0
Thus: = + [when the solute is very soluble in liquid solvent]

3. The term (liquid film control) refers to the resistance lie in the liquid film.
0
Thus: = +

4. The units of mass transfer coeficients are as follows:

= − → =

= ̅ − → ̅ =
. .

= ̿ − → ̿ =
. .

∗ = ̅
m kN
kJ = kN. m = kg. , kPa =
s m

m 1 m kmol m kmol kmol kmol

∗ = ∗ = ∗ = =
∗ = ̿ s kJ
∗K s kJ s kN. m S. kN S.
kN
∗m
kmol. K m
kmol
= = kg
m . kPa. S

̅ ∗ = ̿

m kPa m kPa . kmol m kN kmol kmol

∗ = ∗ = ∗ ∗ =
s kJ s kJ s m kN. m m .s
∗K
kmol. K
= kg

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Example: For a system in which component (A) is transfering from the liquid to the gas
∗
phase, the equilibrium is given by = 0.75 . At one point in the apparturs the liquid
contain 90 mol% of (A) and gas contain 45 mol% of (A). The individual gas film mass
transfer coefficient at this point in the appartus of 0.02716 kmol/m2.s , and 70% of the
overall resistance to mass transfer is known to be encountered in the gas film: determine:

1. The molar flux of (A).

2. The interficial concentration of (A).
3. The overall mass transfer coefficient for liquid and gas phases.

Solution:

1 1
= 0.7
kg KOG
1 1
= 0.7
0.02716 KOG

kmol
K = 0.019
m2 . s

N =K yA ∗ − yA

∗
y = 0.75 x = (0.75)(0.9) = 0.675

kmol
1. N = (0.019) (0.675 − 0.45) = 4.274 ∗ 10−3
m2 .s

2. N =k yA − yA
i

4.274 ∗ 10 = (0.02716)(y − 0.45)

y = 0.607

3. = +
KOG kg kL

.
= +
0.019 . kL

k = 0.0476

1 1 1
= +
KOL H kg kL
1 1 1 kmol
= + → KOL = 0.0142
KOL (0.75)(0.02716) 0.0476 m2 . s

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

The wetted wall column

The wetted wall column is a small experimental device used to determine the average
mass transfer coefficient ( ). Usually it is (1 - 1.5 inch) in diameter and one meter long.

Let the mass transfer being from gas phase to liquid phase:

W =G y −y = L (x −x )

Where:

W : is the total mole rate diffusion along the column.

At one point in the apparatus the diffusion is as follows:

N =K . A . (P − P ∗ ) or N =K . A . (y − y ∗ )

N =W = K . A . (∆y )

W =K . A . ∆P ………….. (kmol/s)

W =K . ∆P ………….. (kmol/m2.s)

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Where:
A is the transfer area (πdL) in (m2).
∆P is the logarithmic mean of partial pressure.

= . . ∆ ………………………. (1)

Now to calculate (K ) from Eq.(1) we must calculate (W ) and (∆P ):

∆P − ∆P
1. ∆P =
∆P
ln
∆P

Where:

∆P = P − P∗ , P∗ = H C

∆P = P − P∗ , P∗ = H C

2. From overall material balance:

W =G y −y = L (x −x )

Where:

y and x : are the mole fraction of component (A) in gas and liquid phase, respectively.

G : is the mole flow rate of gas (kmol/s).

L : is the mole flow rate of liquid (kmol/s).

We can rewrite the Eq.(1) in the mole fraction form instead of partial pressure as follows:

= . . ∆ ………………………. (2)

Where:

∆y − ∆y
∆y =
∆y
ln
∆y
∗ ∗
∆y = y − and = Hx
∗ ∗
∆y = y − and = Hx

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Example: A wetted wall column is used to absorbed NH3 by water from 6 vol.% in air. The
gas flow rate is 1.2 kmol/min at 1 atm and 20oC. Calculate the overall mass transfer
coefficient. The data given are:

 The water flow rate to gas flow rate ratio is 1.4.

 The outlet gas concentration is 1.5 vol.%.
 The column height is 100 cm.
 The column diameter is 2 cm.
 Henry's constant is 1.3.

Solution:

kmol
W =G y −y = 1.2 (0.06 − 0.015) = 0.054
min

W =9 ∗ 10

A = πdL = (3.14) (2*10-2) (1)

A = 0.06283 m2

∆y − ∆y
∆y =
∆y
ln
∆y
∗
∆y = y −
∗
∆y = y −

To find ( x )

G y −y = L (x −x )

G
x = y −y +x
L
1
x = (0.06 − 0.015) + 0
1.4
x = 0.321
∗
= Hx = 1.3 ∗ 0.0321 = 0.04173
∗
= Hx = 1.3 ∗ 0 = 0

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

∗
∆y = y − = 0.06 − 0.04173 = 0.01827
∗
∆y = y − = 0.015 − 0 = 0.015

0.01827 − 0.015
∆y = = 0.0165
0.01827
ln
0.015

W =K . A . ∆y

W 9 ∗ 10 kmol
K = = = 0.868
A . ∆y (0.06283)(0.0165) m .s

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Mass Transfer Coefficient From Empirical Correlation

Several workers have measured the rate of transfer from a liquid flowing down the inside
wall of a tube to a gas passing counter currently upwards. GILLILAND and SHERWOOD
vaporized a number of liquids including water, toluene, aniline and propyl, amyl and butyl
alcohols into an air stream flowing up the tube in order to measure the individual mass transfer
coefficient (kg). GILLILAND and SHERWOOD used the empirical relation below to measure
the individual mass transfer coefficient (kg) and this relation in forms of dimensionless groups:

= .( ) .( )

Where:

Sh: Sherwood number , Sh =

Re: Renold's number , Re =

Sc: Schmidt number , Sc =

kg individual mass transfer coefficient (m/s).

d: diameter (m).

D: diffusivity (m2/s).

ρ: density (kg/m3).

μ: viscosity (N.s/m2).

 When the constants (a), (b) and (c) in the above equation are unknown, then we can
take them as below:

( ) . ( ) .
= .

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Mass Transfer Third Year Dr. ARKAN JASIM HADI

Example: Calculate the gas film coefficient for the absorption of sulfur dioxide from a dilute
mixture with air in a wetted wall column using Gilliland and Sherwood correlation for wetted
wall column for the following data:

 Gas velocity = 2.5 m/s.

 Gas temperature = 293 K.
 Gas viscosity = 1.78 * 10-5 N.s/m2.
 Gas density = 1.22 kg/m3.
 Gas diffusivity = 1.22 * 10-5 m2/s.
 Inside column diameter = 25 mm.

Solution:

. .
Sh = 0.023 (Re) (Sc)

k d 25 ∗ 10−3
Sh = =k = 2049 k
D 1.2 ∗ 10−5

ρ u d (1.22)(2.2)(25 ∗ 10−3 )
Re = = = 3370
μ 1.78 ∗ 10−5

μ 1.78 ∗ 10−5
Sc = = = 1.1959
ρD (1.22)(1.2 ∗ 10−5 )

2049 kg = 0.023 (3370)0.83 (1.1959)0.44

m
k = 0.01129
s

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