CHE 246

SEPARATION PROCESSES

CHAPTER1
MASS TRANSFER
Prepared by:
Mdm Norhafini binti Hambali
[email protected]
LEARNING OUTCOMES
• Define the following terms; Fick’s law, molecular diffusion, mass transfer, mass
transfer coefficient and interphase mass transfer
• Explain the applications of Fick’s law
• Compare and contrast molecular diffusion in gas, liquid and solid
• Determine the flux/ diffusivity of substances in gas, liquid and solid.
• Define and calculate the convective mass transfer of substances.
• Explain the interphases mass transfer and calculate the flux and concentration of
substance at this interface layer.

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TOPICS
1 Introduction To Mass Transfer

2 Fick’s law and molecular diffusion

3 Diffusion through stagnant film and equimolar counter diffusion

4 Molecular diffusion in gas, liquid and solid

5 Convective mass transfer and mass transfer coefficient

6 Interphase mass transfer

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 1.1 INTRODUCTION TO MASS
TRANSFER

Mass transfer is the net movement of a component in a mixture

from one location to another where the component exists at
different concentration

Give examples of mass transfer processes around you ????

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MASS TRANSFER

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6
 DIFFUSION
Species A moves from a region of high concentration to the region
of low concentration

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Molecular diffusion

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1.2 FICK’S LAW AND
MOLECULAR DIFFUSION

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 FICK’S LAW OF
MOLECULAR DIFFUSION

Molecular diffusion: The transfer or movement of

individual molecules through a fluid by means of the
random, individual movement. Applied when the
whole bulk fluid is not moving and diffusion of the
molecules is due to a concentration gradient.

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FICK’S LAW OF MOLECULAR DIFFUSION
dx A
J *
AZ  cD AB
dz
dc A
J *
AZ   DAB
dz
Where;
JAZ = molar flux of component A in the z direction
(kgmol/sm2)
c = total concentration (kgmol/m3)
cA = concentration of A (kgmol/m3)
xA = mol fraction of A
DAB = the molecular diffusivity of the molecule A in B
(m2/s)
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z = distance of diffusion (m)
FICK’S LAW FOR STEADY STATE DIFFUSION
OF A BINARY MIXTURE OF A AND B

Liquid Gas
dx In term of partial pressure
J AZ  cDAB A PV=nRT
dz
P/RT=n/V=c
d (C A )
J AZ   DAB pA1/RT = cA1
dz
c A1  c A 2
cA2
J AZ  D AB
c A1
 dc A z 2  z1
J AZ   D AB zA2 D AB p  p A2
J AZ  . A1
 dz z 2  z1 RT
DAB  p A1  p A 2 
z A1

c A 2  c A1 J AZ 
J AZ   D AB
z 2  z1  z2  z1  RT
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EXAMPLE 6.1-1
A mixture of He and N2 gas is contained in a pipe at 298 K and 1 atm total pressure
which constant throughout. At the end of the pipe at point 1 the partial pressure pA1
of He is 0.6 atm and at the other end 0.2 m, pA2=0.2 atm. Calculate the flux of He at
steady state if DAB of He-N2 mixture is 0.687x10- 4m2/s. Used R=82.06x10-3
m3.atm/(kgmol.K)

Answer: 5.63 x 10-6 kgmol A / sm2 13

TAKE A BREAK
&
REVISION

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1.3 DIFFUSION THROUGH
STAGNANT FILM AND EQUIMOLAR
COUNTER DIFFUSION

SOLID LIQUID GASES

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GASES
Molecular Diffusion

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 EQUIMOLAR COUNTERDIFFUSION IN GASSES

MOL A= pA1 pA2 DAB  DBA

YELLOW

MOL B=
pB1 pB2
PURPLE

PT1 PT2 J AZ   J BZ

pA1 > pA2 and pB2>p B1 dc A dc

J AZ   D AB   J BZ  ( DBA B )
dz dz
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 EXAMPLE 6.2-1
Ammonia gas (A) is diffusing through a uniform tube 0.1 m long containing N 2 gas
(B) at 1.0132 X 105 Pa pressure and 298 K. At point 1, pA1 is 1.013 X 104 Pa and at
point 2 is 0.507 X 104 Pa. The diffusivity DAB=0.230X10-4m2/s.
Calculate the flux JA and JB.

Use R=8314 m3Pa/kg mol.K

Answer:
JA = 4.70 x 10-7 kgmol A / sm2 18
JB = -4.70 x 10-7 kg mol B / sm2
 DIFFUSION PROCESS TOGETHER WITH
CONVECTION

Up to now we consider Fick’s Law for a diffusion in a stationary fluid; that is there
has no net movement or convective flow of the entire phase of the binary mixture A
and B
Diffusion flux JA occurred because of the concentration gradient
JA (kg mol A/s.m2)= vAdCA
vAD = Diffusion velocity of A in m/s
Conversion to a velocity of diffusion;

JA (kg mol A/s.m2)= vAd CA  m kgmolA 

3
s m 
 kgmolA 
= vAd CA  2  19
 ms 
 Now let us consider what happens when the whole fluid is moving in bulk or
convective flow to the right. Component A still diffusing to the right, together
with the moving fluid.
vA Vm = velocity of the bulk relative to a stationary point
VAd = diffusion velocity of A relative to the moving fluid
vAd vm VA = actual velocity of A relative to a stationary point
Then VA = VAd + Vm ……..Eq. 1
CAvA=CAvAd + Cavm ……..Eq.2
Multiplying with CA NA=JA + CAvm ……..Eq.3
total flux of A convective flux of A
diffusion flux of A

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 Let N be the total convective flux ……..Eq.3
N= cvm =NA + NB ……..Eq.4 NA=JA + CAvm
……..Eq.5
vm = (NA + NB )/c

Substituting equation..5 into equation ..3 cA

NA  JA   N A  NB 
NA=JA + CA [(NA + NB )/c] c
dx dx c
J AZ  cDAB A N A  cDBA A  A  N A  N B 
dz dz c
Final equation for diffusion plus convection to use when the
total flux NA is used, which is relative to a stationary point

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 What is the difference between
JA and NA

NA
flux of A relative to stationary fluid, consider a whole system
where there is a moving fluid

JA
flux of A that occurred because of the concentration
gradient, diffusion itself only 22
TAKE A BREAK
&
REVISION

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DIFFUSION THROUGH STAGNANT,
NONDIFFUSING B (GAS DIFFUSION)

Case 1: -Diffusion of A through stagnant or nondiffusing B at steady state.

- One boundary at the end of diffusion path is impermeable to component
B
1) Liquid benzene is stored in a long tube,
with one end of the tube exposed to air.
2) The air inside the tube is stagnant,
and benzene is evaporating through this
stagnant air.
3) The diffusion path is from point 1 at the
gas-liquid interface to point 2 at the
edge of the tube, i.e. across the distance
( z2 - z1 ). 24
DIFFUSION THROUGH STAGNANT, NONDIFFUSING
B (GAS DIFFUSION)

Case 2: NB = 0
1) The ammonia diffuses through the gas mixture from
point 1 in the bulk gas phase to point 2 at the gas-liquid
interface and eventually is being absorbed into water.
2) Air is assumed to be non-soluble in water, hence it
does not diffuse, i.e. it is the non-diffusing component.
3) The diffusion path is the distance ( z2 - z1 ).

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TAKE A BREAK
&
REVISION

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 MOLECULAR DIFFUSION OF GAS
Case 1: Equimolar
Counterdifusion

J AZ  cD AB
x A1  x A 2 c A1  c A 2 DAB  p A1  p A 2 
J AZ  D AB J AZ 
z 2  z1 z 2  z1  z2  z1  RT
Case 2: Diffusion
through stagnant,
non-diffusing B
DAB P DAB P P  p A2
NA   p A1  p A2  NA  ln
RT ( z2  z1 ) p BM RT ( z 2  z1 ) P  p A1
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 EXAMPLE 6.2-2
Water in the bottom of narrow metal tube is held at a constant temperature of 293 K.
The total pressure of air is 1.01325 X 105 Pa and the temperature is 293 K. Water
evaporates and diffuses through the air in the tube and the diffusion path z2-z1 is
0.1524m long. Diffusivity is 0.25 X 10-4 m2/s. Vapor pressure of water at 293 K is
2.341 X 103Pa. Calculate the rate of evaporation.

Use R = 8314.34 m3Pa/kgmolK

Answer: 1.595 x 10-7 kgmol / sm2 30

LIQUID
Molecular Diffusion

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Example diffusion of solutes in liquid:

Liquid-liquid extraction ; Gas absorption ;

Oxygenation of rivers by the air

Since the molecules in a liquid are packed together

much more closely than in gases, the density and
the resistance to diffusion in liquid much greater
 flux in liquid is lower than flux in a gas

Difference of diffusion in gases with diffusion in

liquid 
Diffusion in liquid often quite dependent on
concentration of the diffusing components.
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 EQUIMOLAR COUNTERDIFFUSION
IN LIQUID

Starting from general equation N A  cDBA

dx A c A
dz

c

N A  NB 
For equimolar counter diffusion NA=-NB then the equation become

dx A c A1  c A 2
N A  cDBA N A  D AB
dz z 2  z1
c A1  c A2 DAB cav  x A1  x A 2 
N A  D AB 
z 2  z1 z 2  z1 Diffusion in liquid often
where quite dependent on

concentration of the
    
cav      1  2  2 diffusing components 35
 M  av  M 1 M 2 
 DIFFUSION THROUGH STAGNANT, NONDIFFUSING B (LIQUID
DIFFUSION)
Example: Propionic acid (A) in water (B) solution being contact with toulene
Only propionic acid (A) diffuses through water phase, to the boundary and then into
toulene phase
The toulene – water is a barrier to diffusion of B and NB = 0
DAB cav x  x A2 DAB P P  p A2
NA  ln NA  ln
( z2  z1 ) x  x A1 RT ( z 2  z1 ) P  p A1
D AB cav
NA   x A1  x A2  DAB P
( z 2  z1 ) xBM NA   p A1  p A2 
where
RT ( z2  z1 ) pBM
x B 2  x B1
xBM 
ln  xB 2 xB1 
 1 for dilute solution Diffusion in gases
1 / M 1   2 / M 2 36
cav 
2
MOLECULAR DIFFUSION OF LIQUID
CASE 1: Equimolar CASE 2: Diffusion through stagnant,
Counterdiffusion non-diffusing B
D AB
NA   c A1  c A 2 
 x A1  x A 2  ( z 2  z 1 ) x BM
N A  c avg D AB
z 2  z1
D AB c av
NA   x A1  x A 2 
c A1  c A 2 ( z 2  z 1 ) x BM
N A  D AB
z 2  z1
D AB cav x  x A2
NA  ln
( z 2  z1 ) x  x A1

CHE 246 37
 EXAMPLE 6.31
An ethanol (A)-water (B) solution in the form of a stagnant film 2.0 mm thick at 293 K is in
contact at one surface with an organic solvent in which ethanol is soluble and water
insoluble. At point 1 the concentration of ethanol is 16.8 wt% and the solution density is ρ 1 =
972.8 kg/m3. At point 2 the concentration of ethanol is 6.8 wt% and the solution density is ρ 2
= 988.1 kg/m3. The diffusivity of ethanol 0.74 X 10-9 m2/s. Calculate the flux of ethanol NA
Given:
MA = 46.05 kg/kmol
MB = 18.02 kg/kmol

Answer: 8.99 x 10-7 kgmol / sm2 38

SOLID
Molecular Diffusion

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MOLECULAR DIFFUSION IN SOLID

Diffusion of gases, liquid and solid in solids are generally slower than rates in
liquids and gases.
Example:
The diffusion of phosphorus and boron into silicon
Diffusion of nitrogen or hydrogen in to the rubber
Diffusion of water into foodstuffs
Reaction process, diffusion of solution into the catalyst

There are two types of diffusion in solid :

• Diffusion in solid following Fick’s law (ideal case)
Diffusion in solids does not depend on the actual structure of the solid
• Diffusion in porous solid where the actual structure and void channels are important.
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Does not depend on the actual structure of the solid.
The diffusion occur when the fluid or solute diffusing actually dissolve in the solid to form a homogeneous solution.
Using the general equation

dx A c
N A  cD BA  A  NA  NB 
dz c

The bulk-flow term, CA/CB(NA+NB) is usually small, hence it is neglected

Giving diffusion in solids dx A
N A  cD BA
dz
dC A
NA   D BA
dz
C  CA2
NA  D BA A1
z 2  z1

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DIFFUSION IN SOLID FOLLOWING FICK’S LAW
The solubility of a solute gas (A) in a solid is usually expressed as S

solute m 3 (STP at 1atm and 0 o C)

s
solid m 3 atm

To convert this to CA concentration in the solid kgmolA/m3

1
cA  s x pA x
22.414
solute m 3 (STP at 1atm and 0 o C) kgmolA
 3
x atm x
solid m atm 22.414m 3 (STP )
kgmolA

m 3 solid

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EXAMPLE 6.5-1

The gas hydrogen at 17oC and 0.01 atm partial pressure is diffusing through a
membrane of vulcanized neoprene rubber 0.5 mm thick. The pressure of H 2 on
the other side of the neoprene is zero. Calculate the steady-state flux ,
assuming that the only resistance to diffusion is in the membrane. The
solubility S of H2 gas in neoprene at 17oC is 0.051 m3 (at STP of 0oC and 1
atm)/m3.atm and the diffusivity DAB is 1.03 x 10-10 m2/s at 17oC.

Answer: NA=4.69 x 10-12 kg mol H2/s.m2

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1.3 MASS TRANSER COEFFICIENT

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 MASS TRANSFER COEFFICIENT
Fick’s Law for steady state diffusion of a binary mixture A and B:
dx A DAB
J
Also be written in A   cD AB JA   c A1  c A2 
dz z 2  z1

The value of z2-z1 the distance of the path, is often not known, hence the above
equation simplified and written using a convective mass transfer coefficient , kc'
J A  k c'  c A1  c A 2 

Where:
kc'=constant, kc’=DAB/dz : mass transfer coefficient

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 MASS TRANSFER COEFFICIENT
FOR EQUIMOLAR COUNTERDIFFUSION
 c  c A1  c A 2 
'
Equation for mass transfer : N A k
In liquid - the concentration in terms of mole fraction
In gases – partial pressure
Hence the mass transfer coefficient can be define in several ways equation.
If yA is mole fraction in a gas phase and xA in a liquid phase, then the equation
can be written as follows
N A  k c'  c A1  c A 2   k L'  c A1  c A 2   k x'  x A1  x A 2 

N A  k c'  c A1  c A 2   kG'  p A1  p A 2   k y'  y A1  y A 2 

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 MASS TRANSFER COEFFICIENT FOR EQUIMOLAR COUNTERDIFFUSION

All of these mass-transfer coefficients can be related to each other. For example
Substituting yA1=cA1/c and yA2=cA2/c into the equation

'
 c A1 c A 2  k y
N A  k  c A1  c A 2   k
'
c
'
y  y A1  y A2  k 
'
y    c A1  c A2 
 c c  c

k y'
k 
'
c
c

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 MASS TRANSFER COEFFICIENT FOR A DIFFUSING
THROUGH STAGNANT, NON-DIFFUSING B

xB 2  x B1
k c' xBM 
NA   c A1  c A2   kc  c A1  c A 2  ln( x B 2 / xB1 )
xBM
k c' k
k x'  x
  x A1  x A 2   k x  x A1  x A 2  x BM c
xBM
where
N A  k c  c A1  c A 2   kG  p A1  p A 2   k y  y A1  y A 2 
Gases:
N A  kc  c A1  c A 2   k L  c A1  c A 2   k x  x A1  x A 2 
Refer Table 7.2-1
Liquids:
k c'
HenceN A   c A1  c A 2   k x  x A1  x A 2   k x  c A1  c A 2 
x BMCHE 246  c c 
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CHE 246 49
 EXAMPLE 7.2-1
A large volume of pure B at 2 atm pressure is flowing over a surface from
which pure A is vaporizing. The liquid A completely wets the surface, which
is a blotting paper. Hence the partial pressure of A at the surface is the vapor
pressure at 298 K, which is 0.2 atm. The k’ y has been estimated to be 6.78 X
10-5 kgmol/s.m2.mol frac. Calculate NA,the vaporization rate, k y and kG.

Answer: 7.138 x 10-6 kgmol / sm2 50

CONCLUSION

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 Diffusion in Gases Diffusion in liquid

CASE 1 CASE 1
Equimolar Counterdiffusion Equimolar Counterdiffusion
x A1  x A 2
J AZ  cD AB
z 2  z1
c A 1x  A 2x A 2 
A1c
c A1  c A 2 NN 
A A 
c D D
avg ABAB
J AZ  D AB z 2 z2 z1 z1
z 2  z1

J AZ 

D AB p A1  p A 2 
 z 2  z1  RT

CHE 246
52
 Diffusion in Gases Diffusion in liquid
CASE 2 CASE 2
Diffusion through stagnant, Diffusion through stagnant,
nondiffusing B nondiffusing B

D AB
NA 
D AB P
 p A1  p A2  NA   c A1  c A 2 
RT ( z 2  z1 ) p BM ( z 2  z 1 ) x BM

D AB c av
NA 
D AB P
ln
P  p A2 NA   x A1  x A 2 
RT ( z 2  z1 ) P  p A1 ( z 2  z 1 ) x BM

DAB cav x  x A2
NA  ln
( z 2  z1 ) x  x A1

CHE 246 53
THANKS!
Any questions?

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