Mass Transfer

Chapter 6
Mass Transfer Coefficients and Correlations I
Dr . K. Wegner - Lecture 30.10.2013

30. October 2013

Introduction
Diffusion can be described in two ways:
1. Detailed phisical description based on Fick‘s laws and the
diffusion coefficient.

2. Engineering approach based on the mass transfer coefficient k

Aim of this lecture:

• Introduce the mass tranfer coefficient k

• Give examples how k is used
• Outlook: mass transfer correlations

Mass Transfer – Mass Transfer Coefficients I 6-2

The 'mass transfer coefficient' model assumes that all substances are
well mixed except near the interface. Changes in concentration are
limited to the region near the interface.

Examples:
• Absorption: liquid-gas interface

• Leaching (acid treatment to retrieve metals from ores):

acid solution is homogeneous except near the ore particle
surface

• Digestion: well mixed till the intestine’s wall

Typically the mass transfer model is applicable when we deal with

mass transfer ACROSS an interface.
Mass Transfer – Mass Transfer Coefficients I 6-3
 
Mass transfer model: N1  k 1  c 1i  c 1  k  c 
N1: rate of mass transferred (flux) at the interface
c1i : concentration at the interface of phase A
c1 : concentration in the bulk of phase A
k : Mass Transfer Coefficient (MTC) [cm/s]

N1 includes both diffusion and convection!

Comparison with Fick's first law: j  D  c

D = diffusion coefficient [cm2/s]

Mass Transfer – Mass Transfer Coefficients I 6-4

6.1 Dilute Solutions

Mass Transfer – Mass Transfer Coefficients I 6-5

(a) Example "Humidification"
A 20 liter vessel contains 1 liter of water
at 25 °C. The free surface of the water is
150 cm2.

1. The initially dry air above the water is

5% saturated after 3 minutes. What is
the average flux? (Water vapor
pressure at 25°C = 23.8 mmHg).

2. How long does it take to reach 90%

saturation?

Mass Transfer – Mass Transfer Coefficients I 6-6

Question 1: Average flux?
When no information, assume steady state and set a mass balance:
Amount of water evaporated: N1 × area × time
Water in the air: Air volume × concentration
Water evaporated = water in the air

Area: A = 150 cm2; time: t = 3 min = 180 s

Air volume: V = (20 - 1)L = 19L (neglecting vol. of evaporated water)
Concentration: 23.8 Torr N
0.05   101325 2
n1 p1 760 Torr m
c 1  0.05  c 1,sat  0.05   0.05  
V RT Nm
8.314  298 K
mol K
mol
 0.064
m3
Mass Transfer – Mass Transfer Coefficients I 6-7
Flux from mass balance:
mol
0.064 3  0.019 m3
c1  V m  4 mol
 N1    4.5  10
At 0.015 m  180 s
2
m2  s

How much water evaporated?

~ 3
M 4 mol 18  10 kg mol
V1  N1  A  t   4.5  10  0.015 m  180 s 
2

 m s
2
10 3 kg m3
 2  10 8 m3  0.02 cm3
Mass transfer coefficient (determined from initial state at short times):
 4 mol
4.5  10
N1 m 2
 s 4 m
k   3.5  10 (6.1)
c1,sat  c1 gasphase 0.064 mol  0 s
0.05 m3
Mass Transfer – Mass Transfer Coefficients I 6-8
Question 2: How long does it take to reach 90% saturation?
As time now is in question WE MUST consider the non-steady state
 Accumulati on   Evaporatio n 
    
 in gas - phase   rate 
d  water vapor 
   A  N1
dt  in air 
d
V  c1   A  k  c1,sat  c1 
dt
Boundary conditions: At t=0 c1=0
c1  A  k  (6.2)
Integration with respect to B.C. gives:  1  exp  t
c 1,sat  V 
Mass Transfer – Mass Transfer Coefficients I 6-9
Now solve equation (6.2) for time t (c1=90% saturation):

V  c 
t  ln1  1 
A  k  c 1,sat 

with k from (6.1):

19  10 3
 0.9  c 1,sat 
m 3
t  ln1  

4 m c
0.015 m  3.5  10
2
 1,sat 
s
 8333 s  2.3 h

It takes almost 2.5 hours to reach 90% saturation.

Mass Transfer – Mass Transfer Coefficients I 6-10
(b) Example "Mass transfer in a packed bed"
Consider spherical benzoic acid crystals of 0.2 cm diameter packed
in a bed-like structure. The spheres have a=23 cm2 surface area
per 1 cm3 of bed. Pure water flowing at a superficial (average
through the cross-sectional area of the empty tube) velocity of
v0=5cm/s into the bed is 62% saturated with benzoic acid after
L=100 cm of the bed. What is the mass transfer coefficient?

v=5cm/s

Mass Transfer – Mass Transfer Coefficients I 6-11

Key point: Select the appropriate Δc

Always the difference between the concentration AT the sphere

surface and that IN the solution is selected. However, this c is
different along the bed axis!!

For example, at the entrance of the bed:

N1  k  c 1,sat  0  (6.3)

The flux N1 can be calculated with a mass balance:

Benzoic acid that left the spheres = Amount of acid in the solution

Mass Transfer – Mass Transfer Coefficients I 6-12

Benzoic acid that left the spheres: N1 × exchange area × time

surface area
exchange area   bed length L  cross sectional area A
bed volume
cm2
exchange area  a  L  A  23 3
 100 cm  A
cm
bed length L 100 cm
time   0   20 s
superficial velocity v 5 cm s

Amount of acid in the solution: volume flow × outlet conc. × time

volume flow  v 0  A
outlet concentrat ion  0.62  c 1,sat
Mass Transfer – Mass Transfer Coefficients I 6-13
Combine:
N1  a  L  A  t  A  v 0  c 1  t

cm
5  0.62  c 1,sat
v 0  c1
N1   s 2  1.35  10 3  c 1,sat
a L cm
23 3
 100 cm
cm

Comparing with (6.3): N1  k  c 1,sat  0 

gives k = 1.35 10-3 cm/s

This k is the average MTC, obtained from a mass balance for the
overall ("black box") system.
Mass Transfer – Mass Transfer Coefficients I 6-14
Another way is to write a mass balance on a differential volume
Az in the bed:

v=5cm/s

 flow in   amount 
   
accumulati on   minus    of 
 flow out   dissolution 
   


0  A  c1  v 0  c1  v 0
z z  z
 A  z  a  N 1

where a is the exchange area per bed volume of 23 cm2/cm3

Mass Transfer – Mass Transfer Coefficients I 6-15
Now, N1  k  c 1,sat  c 1 
dc 1 k  a
Divide by Az with z  0:  0 c 1,sat  c1 
dz v

Integrate using boundary conditions: at z = 0 c1 = 0

c1  k a 
 1  exp 0 z 
c 1,sat  v 
This is the local MTC.
v 0  c 1 
Solve for k k ln1  As z increases, c1/c1,sat
a  z  c 1,sat  increases and k decreases.
5 cm s 3 cm
At z=100cm: k ln(1  0.62)  2.1 10
23 cm cm  100 cm
2 3
s
Mass Transfer – Mass Transfer Coefficients I 6-16
(c) Example "Mass transfer in an emulsion"
Bromine is being rapidly dissolved in water. Half
the saturation concentration is reached in about
3 minutes. Bromine is present in the form of
droplets with total surface area A in a volume V
of water.
Mass balance: What is the mass transfer coefficient?

Mass balance:
d
Bromine dissolving: V  c 1 
dt
Bromine leaving the Bromine drops: N1  A  A  k  c1,sat  c1 

Mass Transfer – Mass Transfer Coefficients I 6-17

Combine
d d
Vc 1  A  k  c 1,sat  c 1  or c 1  a  k  c 1,sat  c 1 
dt dt
with a = A / V droplet surface area per unit volume

Integrate this equation with t=0 c1=0

c1
 1  exp k  a  t  Be careful! a=f(t), as the
c 1,sat size of the droplets changes.
1  c 1 
Rearranging k  a    ln1 
t  c 1,sat 
1
  ln1  0.5   0.23 min 1  4  10 3 s 1
3 min
We cannot separate k×a: very important with chemical reactions
Mass Transfer – Mass Transfer Coefficients I 6-18
We have seen that the MTC is not a physical quantity like the diffusion
coefficient. Its value as well as its units depend on the definition for a
specific situation.

Mass Transfer – Mass Transfer Coefficients I 6-19

Mass Transfer Coefficients – Outlook

In the above "scrubber" unit NH3 is separated from a gas stream by

washing the gas with water.
Mass Transfer – Mass Transfer Coefficients I 6-20
1. The concentration difference between bulk and interface is different
along the column. A local MTC should be used.
Local concentration difference → Local mass transfer coefficient
The local k does not change much compared to other variables.
In case there is not sufficient information to determine the local
MTC ("black box"), use the average MTC, as in Example (b)

2. The interfacial area between water and gas is unknown.

Thus, it is difficult to define the flux per unit area.
→ Combine the area with k. Remember our last example (c).

3. Diffusion induced convection will also affect k.

We will address this later in the class. For now we will work
with dilute systems.
Mass Transfer – Mass Transfer Coefficients I 6-21
Example – Averaging the MTC
Imagine a porous solid containing a solution of concentration c1
while the outside concentration is c1

Diffusion will take place (unsteady state) and the flux is (Chapter 2)
D
N1  c1,i  c1, 
t
As a result the local (in terms of a particular time rather than a
particular position) mass transfer coefficient is
D
k1 
t
Note that at t = 0 k1 = 
Mass Transfer – Mass Transfer Coefficients I 6-22
After a long time t0 the average flux can be defined as: N1  k  c 1

How is k related to k ?
t0 t0

 N1dt  D t   c 1dt

D   2  t 0  c 1
N1  0
t0
 0

t0 t0
 dt
0

D
N1  2  c 1
t 0

k  2k

Mass Transfer – Mass Transfer Coefficients I 6-23