1.

2- Mass Transfer Theories

1. The two film theory (Whitmaun,1923)

2. The penetration theory (Higbie, 1935)
3. The surface renewal theory (Dankwerts,1951)
4. The film-penetration theory (Toor and Marchello, 1958)

(1) The two film theory

It states that diffusion is a steady state process and the resistance to mass transfer
lies in two films on both sides of the interface.
It is described by Fick's first law,
P i

dx d
N A = CDAB A = DAB CA Interface
dy dy Ci

CA
PA
XA
yA L1 L2


Gas Liquid
For Gas Phase
DAB dPA
NA =
RT dy
Li
D AB Pi
N A dy = dPA
0 RT PA
D AB
NA = ( PA Pi ) (1.16)
L1RT
For Liquid Phase

dCA
N A = DAB
dy
L2 CA
N A dy = D AB dC A (1.17)
0 Ci

2. The Penetration Theory

It states that diffusion is unsteady state process and the molecules of the solute are
in constant random motion, where clusters of these molecules arrive at the interface,
remaining there for a fixed period of time, and some of them penetrate while the rest
mixes back into the bulk of the phase. The process is described by Fick's second law
with the boundary conditions: CA =0
Gas
Ci
CA 2CA Liquid
= DAB
t y 2

(i) At t=0; C A = C A = 0
y=0
 (ii) At y=0; C A = C i
(iii) At y= ; C A = C A = 0

Putting
y
=
4D AB t

1
=
y 4D AB .t

=
t 2t
C A CA C A
= . = ( )
t t 2t
2C A CA C
= ( ) = . .( A . )
y 2
y y y y
2C A 2 C A 1
= .( )
y 2
2
4D AB .t

C A 2C A
Substitute and in Fick's 2nd law, we have;
t y 2
C A 2C A 1
.( ) = DAB ( )
2t 4 DAB .t
2

d 2C A dC A
+ 2 =0
d 2
d
dC A dP d 2C A
put P = =
d d d 2
dP
And , + 2P = 0
d
dP
+ 2d = 0
P
P
ln P + 2 ln c1 = 0 ln = 2
c
2
P = c1e
dCA 2
= c1e
d
2
dCA = c1 e .d C A = c1erf () + c 2
Where c1 , c 2 are constant
B.C (i) or (iii)
y
erf =
4D AB.t
erf () = 1
0 = c1 (erf ()) + c 2
c1 = c 2

The solution becomes:-

C A = c 2 c 2erf ()
B.C(ii)
0
Ci = c 2 c 2 (erf 0)
c 2 = Ci

The solution is

C A = C i (1 erf )

CA
= (1 erf) = erfc()
Ci
CA
= erfc
Ci

dC A dC
N A = D AB = N A = D AB A
dy dy y = 0
y
But fromC A = Ci (1 erf ) (1.18)
4D AB .t
(
y
)2
dC A 4 D AB .t
= 0 Ci e y =o
dy

dC A
= Ci
dy y = 0
1 D AB
N A = D AB (Ci )( ) = Ci
4D AB .t 4t

NA = Ci
(1.19)
.

3. Surface Renewal Theory

 This is similar to the Penetration theory except that molecules arriving at the
interface remain, there, for different random periods of time. Furthermore in order to
apply this we need to know the rate of renewal of the surface(), which is a very
difficult task and may, only be achieved experimentally.
Mass transfer rates across the interface between two phases (e.g., gas and liquid)
will be enhanced by surface renewal process. Suppose that the surface contains( i)
elements of the surface and a random distribution of ages would exist for each
element. The rate of production of fresh surface is  and that  is independent of the
state of the surface (age of the element of surface).

Suppose that the rate of production of fresh surface per unit total area of surface is,
 and that  is independent of the age of the element in question.
The area of surface of age between t and t+dt will be a function and may be written
as V(t+dt).dt. This will be equal to the area passing in time, dt, from the age range [(t-
dt) to t ] to the age range [t to (t+dt)]. Further, this in turn will be equal to the area in
the age group[t to (t+dt)], less that replaced by fresh surface in time dt:

i.e. V(t+dt).dt = V(t).dt [V(t).dt]..dt

  )  )

= -.V(t)
 ) + .V(t) = 0
V (t) = C. e t
Now the total area of surface considered was unity:

 V (t) dt = 1
 ) 
 C. e  dt = 1
t
C 
  
= 1, C=

V(t) = . e t
Substitute this result in the solution of the penetration theory (equation 1.19), which
is:

NA = Ci
to get,
.

) D
NA = Ci  )
4.t
AB
. e( dt


NA = Ci


 t /+ e( dt

Putting, .t = x2 . Then .dt = 2xdx. Substitute in above,
(.
NA = Ci

 .
. 2.  e- dt

NA = Ci D. (1.20)

4. The Film Penetration Theory

As the name suggests it is a combination of the Film and Penetration theories. The
governing system of equations is,
 CA 2CA
= DAB
t y2
(i) At t = 0; C A = C A = 0
(ii) At y = 0; C A = C i
(iii) At y = 0; C A = C A = 0
Giving the solution thus,

1 +789) ;+7)89<
= 7)
7) erfc - 7)
7) erfc (1.21)
12 + : . + : .

And the mean mass flux.

 7. 8.
NA = CAi
{1 + 2 7)
7) exp @ ) (1.22)
=.  .

1.3- Mass Transfer Coefficient

Interface
Gas side
D
N A = AB (PA Pi )
L1RT Gas
PA Liquid
P Pi Pi
NA = kg ( A )
RT Ci
N A = k g (C A C i )
g g
CA
L1 L2
N A = Ck g (y A y i )

Where y A and y i are mole fraction in gas phase y=0

Liquid side

D AB
NA = (Ci C A )
L2
D AB
NA = C (x i x A )
L2
N A = Ck l (x i x A )

Where x i , x A are mole fractions in liquid phase.

kG: Individual mass transfer coefficient in gas phase
kL: Individual mass transfer coefficient in liquid phase
In the above we replaced (DAB/L1RT) by kg and (cDAB/L2) by kl because L1and L2
can not be estimated theoretically or experimentally.
1.3.1-Overall Mass Transfer Coefficient

In the previous section the equations obtained are not useful for practical
purposes, since the concentrations at the interface (Pi and Ci) can not be determined
therefore we resort to concept of overall mass transfer coefficient. This is defined as,
For gas phase: NA = KG (PA PA*)
For liquid phase: NA = KL (CA* - CA)
Where (*) refers to the equilibrium value.
Or y A* = mx A (PA = HC A )
Where m is equilibrium constant.
Also Pi = H.C i
Or yi = mxi

1.3.2-Relation between overall and individual M.T.C

N A = k g (y A yi ) .. (i)
N A = K G (y A y A )
*
(ii)
N A = k l (x i x A ) (iii)
NA = K L (x*A xA ) (iv)

From equation (i) & (ii),

 9  9C )
=
AB DE 9  92)
Adding and subtracting yi to the numerator in LHS.,
(yA yA ) + yi yi
*
1
=
KG k g (yA yi )
(y A yi ) (y y A )
*
1
= + i
K G k g (y A yi ) k g (y A yi )
Using yA= mxA & yi= mxi and that NA=kg(yA-yi)=kL(xA-xi)
1 1 m(xi x A )
= +
K G k g k l (x i x A )

1 1 m
= + (1.23)
KG kg kl

1 1 1
Excercise; Prove that = + (1.24)
K L mk g k l

1.3.3- Volumetric mass transfer coefficient, KG.a and KL.a

When using KG or KL we need to find the interfacial (a), which is defined as.
a = 6* F/dav.
Where is the fractional hold ( fraction of bubbles or drops in the column) and dav.is
the average bubble or diameter. Thus in order to estimate (a) we have to use
correlations for F and dav and, although there are many correlations in the literature,
they are inadequate and unreliable. The best ones gives an error of nearly 70%, some,
even, gives as much as 3000% error !. Therefore the use of the combined form ( KG.a
or KL.a) is, clearly advantageous.
And researchers should be working along these lines i.e., finding correlations for
the volumetric mass transfer coefficient rather than the film or overall coefficients.

1.4-The Wetted Wall Column

This is simple apparatus to measure the average M.T.C it usually consists of a tube
about 1 m in length and 2 cm in diameter Gas out
y2
We have the equation,
Liquid in
N A = K G (y A y A ) kmole
*
2 x2
m .s
The mole rate (WA ) = N A * A = K G .A.(y A y A ) kmole/s
* z
A = .d.z Gas in
(1.25)
WA = G1 (y1 y 2 ) = L(x1 x 2 ) y1

For the driving force ( y A y A* ) we take the average value for the whole
Liquid out
column and this is may be represented bythe log mean driving force:- x1

(y ) (y yA
*
) (y yA
*
)
A yA =
(y )
* A 1 A 2
(1.26)
yA
L.m *

(y )
A 1
Ln
yA
*
A 2

y = mx1
*
1
And (1.27)
y2 = mx2
*

The final equation is,.

(y1 y1 ) (y 2 y 2 )
* *
WA = K G (.d.z) = G1 (y1 y 2 ) (1.28)

*
(y1 y 1 )
Ln

*
(y 2 y 2 )

Example 5: A wetted wall column is used to absorb Ammonia by using pure water
from (6%) by volume mixture with air . The gas flow rate is (1.2 kmol min) at 1atm
and 200C. Calculate the overall mass transfer coefficient. Data given :
The ratio of water to air flow rate = 1.4
The outlet ammonia concentration = 1.5% by volume
Column diameter = 2 cm
 Column height = 100 cm ; and Henery s constant, m = 1.3

Solution:
Find x1 using equation (1.25),
8
y1 y2 = (x1 x2)
G
0.06 0.015 = 1.4 (x1 0)
x1 = 0.032
From equation (1.26),

L.LM.
J.K N.M O .P)
(yA - HIC )Lm = L.LM.
JL.LQR O
N.M
87 L.LNSRL)
= 0.0238
Finally, from equation (1.28),

KG (3.14*2*100).(0.0238) = (1.2).(0.06 0.015)

KG = 3.61*10-3 kmol/cm2.min

Calculation of Mass Transfer Coefficient

1 1

Sh = 2 + 0.6 Re .Sc 2 3
(1.29)
1 1

Sh = 0.023 Re .Sc 2 3

D.T
Where Sh is the Sherwood number =


U.V.T
Re is the Reynolds number =

Sc is the Schmidt number =
U.
And k is the mass transfer coefficient.

1.5- Diffusion with Chemical Reaction

Consider gaseous (A) diffusing through liquid (B), which contains a solute (C).
(A) reacts with( C) according to a first order irreversible reaction , with a reaction
constant k1.

A k1 AC

Refer to the accompanying figure to perform material balance on (A) over elemental
Xz,
In = Out Gas A
TY
NA.S = ( NA + . Xz).S + k1.S.Xz.CA
TZ
(S: cross sectional area)
TY
= - k1.CA
TZ
T1
But NA = - DAB NA
TZ
T+1
DAB - k1 C A = 0 Xz AAC
TZ.
T+1
(k1/DAB ).CA = 0 NA+(dNA/dz).Xz
TZ.
The auxiliary equation is,
m2 - k1/DAB = 0 Liquid B
m1 = :k /D]^ and m2 = @:k /D]^
The general solution is,
CA = _.exp[:k /D]^ .z] + `.exp[@:k /D]^ .z]

Using the boundary conditions,

B.C. 1: at z = 0, CA = CA0
T1
B.C. 2: at z = L, NA = 0 or =0
TZ
The final solution is,

e
1 abcd :DN 8. / ;J O<
f
=
1L abcd:DN 8. /