Mass Transfer

Theories for Mass Transfer Coefficients

Lecture 9, 15.11.2017, Dr. K. Wegner
9. Basic Theories for Mass Transfer Coefficients
Aim: To find a theory behind the empirical mass-transfer correlations
(e.g. Tables 8.3-2 and -3 in Cussler’s book) that is based on
physics (first part of this class). Such models should connect
mass transfer and fluid flow.

We would like to predict the mass transfer coefficient k as a function

of the diffusion coefficient D and the fluid velocity v.

First, we look at MTC’s for fluid-fluid systems (9.1) that are VERY
important in industrial applications.
In the following lecture we investigate models for simple fluid-solid
interfaces (9.2) that can be rather elaborate and detailed but have
limited application in industry.
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-2
9.1 Fluid-Fluid Interfaces, e.g.
Gas bubbles in Liquid in
Falling film
tank packed tower

Source: Cussler, Chapter 2.5.2 Source: Wikipedia, “Blasensäule” Source: Büchi Glas, Uster
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-3
 Gas bubbles in Liquid in
Falling film
tank packed tower
Evaporation, Aereation, Extraction,
Gas scrubbing Gas ab- and desorption, Distillation
Bioreaktors
From Table 8.3-2:
0 .5 13 13 0.67
 z ⋅ v0   v0 
0 .5
 d3 ⋅ g ⋅ ∆ρ / ρ   ν   1
13
D
kz
= 0.69 ⋅  
kd
= 0.31⋅     k   = 0.0051    (ad)0.4
ν  D  νg   aν  ν
2
D  D  D 

k ~ D0.5, ~v0.5 k ~ D2/3 k ~ D0.5, ~v0.67

Why is k ~ D1/2 or k ~ D2/3 or k ~ v0.67 ??

Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-4
9.1.1 The
9.1.1 TheFilm Theory
Film (Nernst,
Theory 1904)1904)
(Nernst,

Assumptions:
- All action (fluid flow and mass transfer) occurs in a thin film at the
interface
- Bulk fluid (e.g. gas) – FILM – bulk fluid (e.g. liquid)
- Steady-state flux across film
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-5
 n1 z =0 = N1 = k (c 1i − c 1 ) (9.1-1)

This flux can be obtained also in terms of D

(for dilute concentrations)
D
=
N1 j1=
z =0
(c1i − c1 ) (9.1-2)

D
Comparing equation (7.1) and (7.2) gives k = (9.1-3)

k
Or by rewriting gives = 1= Sh (9.1-4)
D
This simple theory gives k ∝ D1 BUT all fluid characteristics (e.g.
fluid velocity due to stirring) are in the unknown film thickness  .
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-6
This simple theory provides the FRAMEWORK of most MTC’s
as follows:

 mass transfer   characteristic 

     other 
Sh = coefficient   length  F  system 
 diffusion   
 variables 
   
 coefficient 

Applications:

The film theory is used in some practical cases to determine the  .

Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-7

Example:
CO2 is being scrubbed out of a gas by water flowing through a
packed bed. Calculate the film thickness if 2.3·10-6 mol/(cm2∙s) of
CO2 are adsorbed when
pCO2= 10 atm, H = 600 atm and DCO2/H2O= 1.9·10-5 cm2/s.

Solution:
First find the interfacial concentration c1i :
c1i
p1 =H ⋅ x1 =H
c
 c1i 
10 atm 600 atm  3 
⇒
 (1 mol)/(18 cm ) 
c1i = 9.3 ⋅ 10-4 mol/cm3
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-8
Calculate k from equation (9.1-1):
=
N1 k(c1i − c1 )

2.3·10-6 mol/(cm2 s) = k (9.3·10-4 mol/cm 3 - 0)

k = 2.5·10-3 cm/s

Now
D 1.9 ⋅ 10 −5 cm2 / s −2
=
 = −3
= 0.76 ⋅ 10 cm
k 2.5 ⋅ 10 cm / s
2

Typically  ≅ 10 −2 cm ← VERY IMPORTANT

Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-9
9.1.2 The Penetration Theory (Higbie, 1935)
Assumptions:

• Same as in “Film-theory” but the film

is VERY thick
• Diffusion is important in z-direction
• Convection is important in x-direction

Equation (9.1-1): =
N1 k(c1i − c1 )

The solution to this problem was given before in the context of the
semi-infinite slab (Cussler p. 46):
=
N1 j1=
z =0
Dv max / (π x ) (c1i − c1 ) (9.1-5)
where N1 is the flux and vmax is the velocity of the liquid at the interface
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-10
Note that this flux at the interface is valid at a specific x. To find the
average flux, N1(x) has to be averaged over the entire surface:
L W
1
=N1 ∫ ∫
W ⋅L 0 0
n1 z=0 dy ⋅ dx

where L is the length of the film in x and W is its width in y. Since n1

does not vary in y, inserting 9.1-5:
L
1 D ⋅ v max 2 D ⋅ v max ⋅ x
→
L
N1 = ∫ ⋅ ∆c dx N1 = ∆c
L0 π⋅x L π 0

2 D ⋅ v max ⋅ L
N1 = ⋅ ∆c
L π
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-11
 D ⋅ v max
or =N1 2 ⋅ ( c1i − c1 )
π ⋅L
D ⋅ v max
so k = 2⋅ (9.1-6)
π ⋅L

The L/vmax is called contact time and is not known a priori in

complex situations, as was  in the film theory.

Compare: k ∝ D1/2 (penetration theory)

k ∝D (film theory)

Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-12

These two theories bracket the experimental data (Table 8.3-2) very
well, almost too well to be accepted.
Equation 9.1-6 can be rewritten, assuming that the average velocity
is v0 = 2/3 vmax (true for a laminar slit flow of a Newtonian fluid).
1 1 1
L L 3 2  Dv 0
 6 2  Lv 0
 2
k =2     =    
D D2  πL  π =  D 
1 1 1
6 2  Lv 0
 ν 2 2
=     
π  ν  D
1
6 2
=   Re1 2 Sc1 2
 π  1

Pe 2

Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-13

9.1.3 The Surface Renewal Theory (Dankwerts, 1951)
The success of the penetration theory with data despite its restrictive
assumption motivated scientists and engineers to propose alternative
and more realistic models leading, however, to the same variable
dependencies at the end.
Assumption:
The thick film framework is replaced
by TWO regions: interface and bulk.
In the interfacial region mass transfer
takes place according to penetration
theory. Then elements of this region
ARE EXCHANGED with the bulk
region. This is the so-called surface-
renewal process.
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-14
The issue is how long the fluid elements stay in the interfacial region
“exposed to penetration”.

 probability of a surface 
 
E(t)dt=  element to be at the 
 surface for time t 
 

∞
E(t) is the residence time distribution, RTD, and ∫
0
E(t) dt = 1

The transfer of interfacial elements into the bulk is random and any
surface element is equally likely to be withdrawn.

Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-15

By definition the fraction of surface elements at time t is :

=θ exp [ −t / τ ]

where τ is a characteristic constant equivalent to the average

residence time of an element in the interfacial (surface) region.
∞
Now the fraction θ is also the sum of probabilities θ = ∫ E(t) dt
t

Thus the residence time distribution of surface elements is:

 
 ∞
  ∞ 
dθ  t d
t
 ∫ E(t )dt  =  = −E(t ))
d 1
dt  t  dt

= −
τ
exp

−
τ


=
dt  ∫ E( t )dt − ∫ E( t )dt

0
  0

 =1 
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-16
 1  t
So, E( t ) = exp − 
τ  τ

The mass transfer coefficient at the interfacial region is obtained

from the semi-infinite slab model (see eq. 9.1-5 and Cussler p. 46)
as:

⋅ (c 1i − c 1 )
D
n1 z =0 = N1 =
πt

The semi-infinite slab model is used here even though the

interfacial region is not infinite. But if the surface is rapidly renewed
and the τ is small, then the interfacial region appears as infinite.

Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-17

The average flux (over all surface elements) is:
∞
N1,av = ∫ E( t ) ⋅ n1 z =0 dt
0
∞
 exp[− t τ] D 
= ∫  ⋅ ⋅ (c 1i − c 1 ) dt
0
τ πt 

D (c 1i − c 1 ) exp[− t τ]
∞
= ⋅∫ dt
π τ 0 t

=
D (c 1i − c 1 )  π ⋅ erf t τ 
⋅
( ) ∞

π τ  1 τ 
 0
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-18
 D (c 1i − c 1 )  
N1,av =
π τ   
(
⋅ πτ ⋅  erf ∞ τ − erf 0 τ 

) ( )
 =1 =0 

N1,av =
D
(c1i − c1 ) Thus, k= D /τ
τ

As in the penetration theory, here k ∝ D1/2

Again the residence time τ is as unknown as the  in film theory
or the L/vmax (contact time) in the penetration theory.
The major contribution of the surface renewal theory is that it
gives a more REALISTIC physical situation. This gives a better
starting point for development of effective correlations and better
models.
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-19
Summary:
Advantages Disadvantages
The Film Theory
Simple; Film thickness 
k good base for is unknown
=1 extension
D
The Penetration Theory

D ⋅ v max Simplest Contact time

k = 2⋅ including flow (L/vmax) usually
π ⋅L unkown

The Surface-Renewal Theory

Similar math to Surface-renewal
k= D /τ penetration theory, rate (τ) is
but better physical unknown
picture
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-20
The dependencies of k on D and v, like k ~ D1/2, k ~ D2/3 or k ~ v0.67,
observed in the experimentally-based MTCs are typically not well
reflected by the simple mass transfer models.

These simple models for fluid-fluid interfaces pretend that fluid

motion is incorporated in diffusion and everything is treated as a
thin film or semi-infinite slab problem.

In principle, these two extreme cases should bracket all possible

geometries. Yet, especially the effect of flow (velocity) is usually
not well reflected.

One reason is that the simple theories assume a homogeneous

system while real systems are heterogeneous with respect to
concentration and flow (Schlünder, 1977).
Schlünder E.U., Chem. Eng. Sci. 32, 845-851.
Mass Transfer – Basic Theories for Mass Transfer Coefficients 9-21