Mass Transfer

Mass Transfer Coefficients (MTC) and

Correlations II

1
7.2-1
Correlations of Mass Transfer Coefficients
Mass transfer coefficients (MTCs) are not physical properties like the
diffusion coefficient. They differ from case to case and even within a
system, depending on their definition.

With the help of experimental observations, correlations for mass

transfer coefficients have been developed for standard cases
(e.g. fluid flow through a packed bed of particles, gas bubbles rising
in a tank, falling films, flow over surfaces and within tubes, …).
Such MTC correlations are typically expressed with dimensionless
numbers, frequently in the following form:
X Y
kd  dv    
 C    Sh  C  Re   Sc 
X Y
or
D    D 2
7.2-2
 Convective heat transfer h  l
Sh  Nu  
Conductive heat transfer 
Equivalent in heat transfer
h: convective heat transfer coefficient
λ: thermal conductivity
diffusivity of momentum
thermal diffusivity Pr is the equivalent to Sc
in heat transfer
α: thermal diffusivity

Dimensionless numbers
Table 8.3-1 from Cussler, 3rd3 ed.
7.2-3
Selected mass transfer correlations for fluid-fluid interfacesa

Table 8.3.-2 from Cussler

4
7.2-4
Selected mass transfer correlations for fluid-solid interfacesa

5
Table 8.3.-3 from Cussler 7.2-5
 MTC Correlations
Excellent for preliminary design of small pilot plants. For design of full scale
equipment you must supplement them with data of the SPECIFIC chemical system.

Fluid-Fluid interface Fluid-Solid interface

MTC error at best 30%
The MTC is expressed mostly as
k flow in a single tube. This high accuracy
kl
Sherwood-#  or a Stanton-# 
D 
The Sh is typically expressed by powers of
Re and Sc corresponding to “convection”
and “diffusion”, respectively.
When the convection is not a typical
”forced” one but one generated by density
gradients, it is “free convection” and the
Re is replaced by the Grashof-#.
The error is about 10% and as low as
1% especially when dealing with laminar
is attributed to the heat transfer origin of
these correlations and the fact that
SIMPLER geometries are involved. Also
heat transfer is an older subject than
mass transfer. For example, laminar
flow of one fluid in a tube is much better
understood than turbulent flow of gas
and liquid in a packed tower!
Again the MTC is written in the Sh- or
St-notation. 6
7.2-6
Example: Dissolution rate of a spinning disk
Remember from “Generalized Mass Balances” :
“A solvent flow approaches a spinning
disk made out of a sparingly soluble
solute. Calculate the diffusion-
controlled rate at which the disk
slowly dissolves at steady state.”
→ The diffusion flux is:
c1  D2 / 3 1/ 2 
j1 z0  D 
z 0  0.62 
 c1(sat)
z 1 / 6 
  
1/ 2
D  d2  
1/ 3

 j1  0.62     c1(sat)
d   D
D
 j1  0.62 Re1/ 2 Sc1/ 3c1(sat)
d 7
7.2-7
Now:
A solid disc of benzoic acid (BA) 2.5 cm in diameter is spinning at
20 rpm and 25°C. How fast will it dissolve in a large volume of a)
water and b) air?

DBA/W =10-5cm2 /s
DBA/A =0.233cm2 /s

Solubility of benzoic acid in water is 0.003 g/cm3.

Equilibrium vapor pressure of benzoic acid in air is 0.3 mmHg at 25°C.
The molecular weight of BA is 122 g/mol.

Will the mass transfer be faster in air or in water?

8
7.2-8
 1/2 1/3
    
From Table 8.3.-3: k  0.62D     and N1  kc1(sat)
   D
a) For water 1/3
cm  20 / 60  2 / s   0.01cm / s 
2 1/2 2

k  0.62  10 5  0.9  103 cm / s

s  0.01cm2 / s   10 5 cm2 / s 
N  0.9  10 cm / s  0.003g / cm
1
-3 3
 2.7  10-6 g / cm2s

b) For air 1/3

cm  20 / 60  2 / s   0.15cm / s 
2 1/2 2
k A  0.62  0.233    0.47cm / s
s  0.15cm2 / s   0.233cm2 / s 

 0.3mmHg 1mol 273 122g 

N1  0.47cm / s     0.9  10 6
g / cm2
s
 760mmHg 22.4  10 cm 298 mol 
3 3

The flux in air is 1/3 of that in water even though the k in air is 500
times that in water. 9
7.2-9
Mass Transfer across Interfaces (very important)
Often we encounter the following scenario: Bulk  interface  Bulk

Basic equation: N  Kc

1 1

where K is the overall MTC and c1 an APPROPRIATE

concentration difference and most notably the equilibrium or
asymptotic concentration.
Case a: Heat transfer
Hot benzene on cold water.
The benzene cools while the water
warms until they reach the same T.
Equal T is the criterion for equilibrium.
The amount of energy transferred is
No problem!
always equal to the T. 10
7.2-10
Case b: Bromine extraction
A benzene solution of bromine is placed Bromine concentration:
on top of a water solution containing the
SAME concentration of bromine.
Later the initially equal concentrations
have CHANGED and the Br
concentration in C6H6 is higher than in
H2O. Why?
→ Bromine is more soluble in C6H6 than in H2O.
Now the c1 here should be: c1= c1(in benzene) - Hc1(in water)
Otherwise the initial c1 is zero and we still have flux.
 concentration of Br in benzene 
The partition coefficient H is: H=  
 concentration of Br in water at equilibrium
11
7.2-11
Case c: Bromine vaporization
Initially Br evaporates from water
into air. Initially the Br concentration
in water is higher than that in air; at
the end it is lower.

This might be a problem of units: Concentrations in the liquid are

expressed in mol/L and those in air by the partial pressure ??

Mass transfer should be described in terms of the more

fundamental chemical potentials. If this was done, the
concentration difference would disappear.

12
7.2-12
7.4 The Overall MTC
The flux in the gas is:

N  k (p  p )
1 p 10 1i
(4)

Because the interfacial region

is thin, it is at steady state.
Thus, the flux will be equal to
that in the liquid.

N  k (c  c )
1 L 1i 10
(5)

where kP and kL are the gas and

liquid MTC’s!
So, kP p10  p1i   kL c1i  c10 
13
7.2-13
Always we must remove the dependency on the interfacial
concentration or partial pressures, as these are difficult to determine.
Usually there is equilibrium at the interface:

p1i kP  p10  kL  c10 H is Henry’s constant or

c1i   c1i  the partition coefficient (6)
H kP  H  kL in the simplest case

So the flux N1 from equation (5) should be derived as:

1
N  (p  Hc ) (7)
1/ k  H / k
1 10 10

p L

1
KP  is the “overall gas-side MTC”
1 kp  H kL
14
7.2-14
Analogy with electric circuits:
“Voltage difference”
“Current”

N1 
p10  Hc10 
1 kP  H kL

“2 resistances in series”

Many times the engineer’s job is to determine which is the rate

limiting resistance: in the gas or the liquid ??

15
7.2-15
Now we can write the flux equation in two ways:

A) N  K (p  p *) where K 
1 and p *  Hc
1/ k  H / k
1 p 10 1 p 1 10

p L

KP is the “overall gas-side mass transfer coefficient” and p1* is the

hypothetical gas-phase concentration that would be in equilibrium
with the bulk liquid concentration.
1
B) N  K (c * c ) where KL  and c *  p / H
1 L 1 10
1/ kL  1/ k pH 1 10

KL is called the “overall liquid-side mass transfer coefficient” and

c1* is the hypothetical liquid concentration in equilibrium with the
bulk gas concentration.

16
7.2-16
Example : Oxygen Mass Transfer
Estimate the overall liquid-side MTC for O2 transfer from water into
air assuming that each MTC is k = D/0.01 cm, Henry‘s law constant
is H = 4.4×104 atm, Dair = 0.23 cm2/s and Dwater = 2.1×10-5 cm2/s.
Goal: Calculate kL and kP and substitute in the appropriate equation.

D 2.1 10 cm / s5 2

k 
L
L
 2.1 10 cm / s
3

0.01cm 0.01cm
Finding kP and H is more difficult for unit conversion
k D
k 
p
 G G

RT (0.01cm)RT
0.23cm / s 2

  9.4  10 mol / (cm  s  atm)

4 2

(0.01cm)(82cm  atm / (mol  K))(298K)

3

17
7.2-17
From the way H’ is given (unit consistency)

H` 4.4  104 atm

H  3
 7.9  105
atm  cm3
/ mol
c 1 mol / 18 cm

Insert these values into the equation for KL

1
KL 
1/ kL  1/ k p H
1

1/ (2.1 10 cm / s)  1/ (9.4  10 mol / cm s  atm  7.9  10 cm  atm / mol)
3 4 2 5 3

 2.1 10 cm / s
3

The mass transfer is dominated by the liquid-side resistance!!

18
7.2-18
Example : Perfume Extraction
Jasmone (C11H16O) is a valuable aroma from jasmine flowers that
is used in soaps and cosmetics. We are recovering this from its
water solution (jasmine flowers in water) with benzene drops the kB
=3.0 x 10-4 cm/s while kW = 2.4x10-3 cm/s

However, jasmone is 170 times more soluble in C6H6 than in H2O.

What is the overall MTC?
Assuming steady state
N1 = k W (c10 W - c1iW ) = k B (c 1iB - c 10B ) (8)

The interfacial concentration is in equilibrium, so:

c1iB  H  c1iW (9)

19
7.2-19
Eliminate the interfacial concentration using equations 8 and 9:
k c
W 10 W
k cW 1iW
 k Hc  k c
B 1iW B 10 B

c k c k c
k c k c  ( k  k H )c → c 1iW   1 iB W 10 W B 10 B
(10)
W 10 W B 10 B W B 1iW
H k k H W B

Replace this in the N1 for benzene

 k W c10 W  k Bc10B 
N1  k B  H - c10B 
 k W  k BH 
 Hk c  Hk c  k c  Hk c  kk
k  W 10 W B 10 B W 10 B B 10 B
 (Hc
B W
c )
k k H  k k H
B 10 W 10 B

 W B W B

 1 
  (Hc  c )
 1/ k  H / k 
10 W 10 B

B W
20
7.2-20
The overall MTC, K´ is
1
K' 
1/ (3.0  104 cm / s)  170 / (2.4  10 3 cm / s)

 1.3  105 cm / s

Again the mass transfer in water controls the process because

jasmone is more soluble in C6H6.

21
7.2-21