COLLEGE OF ENGINEERING

CENTRAL PHILIPPINE UNIVERSITY

ILOILO CITY, PHILIPPINES
Tel. Nos. (033) 3291971 (to 79) Local 1085
Fax No. (033) 3203004
Email: chem._engg@cpu.edu.ph

MODULE 3
MASS TRANSFER
Introduction

Mass transfer is the net movement of one material component in a mixture from one
location to another where components exists at a different concentration.

Mass is transferred from one phase to another distinct phase; however, the basic
mechanism is the same whether the phases are gas, solid or liquid.

Applications of mass transfer can be found in separation processes such as gas

absorption, liquid extraction, distillation, adsorption, leaching, chromatography, mixing, etc.
In some cases, as in humidification and dehumidification processes, simultaneous heat and
mass transfer are important.

Mechanism of Mass Transfer

There are basically 2 general modes or mechanism of mass transfer:

1. Mass Transfer by Diffusion:

 Diffusion/convection

a. Diffusion is analogous to conduction in heat transfer

convective heat and convective mass are the same

transfer transfer
b. In diffusion, the transport is by random molecular motion

Categories of Diffusion:

1. Molecular diffusion

- is the random and spontaneous microscopic movement of molecules as a

result of thermal motion

2. Eddy diffusion

- is the random macroscopic fluid motion caused by the eddy motion

characteristic of turbulent flow.

Mass Transfer by Convection

This uses the motion of fluids to transfer heat. This involves the energy exchange
between a surface and a fluid.
 1) natural convection
- refers to a case where the fluid movement is created by the warm fluid itself

2) forced convection

- uses external means of producing fluid movement

Distinct Differences of Transport of Matter and Heat Transfer

I.Non-fundamental
Mass Transfer Heat Transfer
Difference

a. Interface between 2 media

usually mobile non-mobile
which matter is transferred

Example: gas-liquid interface usually a solid wall

I. Non-fundamental Mass Transfer Heat Transfer

Difference

a. diffusivity coefficient At 20°C Thermal diffusivity (  ) is

2
much larger than diffusion
Gas D  105 m coefficient D
s
2
9
Liquid D  10 m
s
2
Solid D  1010 to 10 15 m
s
the penetration of matter the penetration of heat (and
takes place over small momentum) takes places
distances over relatively greater
distances

convective transport occurs convective transport

at low velocities; convective exceeds diffusion transport
transport exceeds diffusion at high velocities
transport
I. Principles of Mass Transfer

A. Similarity of Mass, Heat and Momentum

1. Heat Transfer Processes

Momentum transfer - occurs in fluid flow, mixing, sedimentation, filtration

Heat transfer - occurs in conductive and convective transfer of heat, evaporation,
distillation and drying.
Mass Transfer - occurs in distillation, absorption, drying, liquid-liquid extraction,
adsorption, ion-exchange crystallization and membrane processes

2. General Molecular Transport Processes

momentum, heat, and mass - are characterized by the same general type of equation

Example

A drop of blue liquid dye is added to a cup of water. The dye molecules will diffuse
slowly by molecular diffusion to all parts of the water.

To increase this rate of mixing of the dye, the liquid can be mechanically agitated by
a spoon and convective mass transfer will occur.

The modes of heat transfer, conduction, and convective heat transfer, are
analogous to molecular diffusion and convective mass transfer.

First, we will consider the diffusion of molecules when the whole fluid is not moving
but is stationary. Diffusion of the molecules is due to a concentration gradient.

The general Fick’s Law can be written as follows for a binary mixture if A and B:
* dX A
J AZ  CDAB  equation 1
dz
where

A B
C = total concentration of A and B in kgmol
m3

X A = mole fraction of A in the mixture of A and B

If C is constant: C A  C X A

CdX A  dCX A  dC A equation 2

substitute eq. 2 in eq. 1
* dC A
J AZ   DAB 
dz
where

J AZ = molar flux of A in z direction

DAB = diffusivity or diffusion coefficient

dC A
= concentration gradient of A in z direction
dz

Example:

A mixture of He and N2 gas are contained in a pipe at 298K and 1atm total pressure
which is constant throughout. At one end of the pipe at point 1, the partial pressure PA of He
is 0.6atm and the other end, 0.2m20cm  PA2  0.2atm . Calculate the flux of He @ steady
2 2
state if DAB of the He-N2 mixture is 0.687 104 m ( 0.687 cm ).
sec sec

Solution:

Since the total pressure is constant, then C is constant, where C is obtained using
ideal gas law (IGL)

PV  nRT

n P
C 
V RT
where

n is the kgmole A plus B

V is volume in m3
T in K
m3 Pa m3atm
R  8314.3  82.057 103
kgmole  K kgmole  K
C kgmole A plus B/m3

In cgs:

cm 3atm
R  82.057
gmole  K
For steady state, the flux
*
a. J AZ is constant

b. DAB for a gas is constant

* dC A
J AZ   DAB
dz
z2 C A2
*
J AZ  dz   DAB  dC A
z1 C A1

*
J AZ 

DAB C A1  C A2 
z2  z1

Also, from IGL:

PA1 nA
C A1  
RT V
*
J AZ 

DAB PA1  PA2 
RT z2  z1 

Partial Pressure are

1.01325 105 Pa
PA1  0.6atm 
atm

1.01325 105 Pa
PA2  0.2 
atm
Using SI units

*
J AZ 
0.687 10 6.08 10
4
 2.027 104
4

83142980.2  0
* kgmolA
J AZ  5.63 106
s  m2
Note: Other deriving forces (besides concentration difference) for diffusion also occur
because of T, P, electrical potential and other gradients.
Convective Mass-Transfer Coefficient

When a fluid is flowing outside a solid surface

fluid
solid surface

We can express the rate of convective mass transfer from the surface to the fluid or vice
versa by the equation.


N A  kC CL1  CLi 
Note: we use

J A to represent the diffusion flux relative to the moving fluid

N A to represent the total flux of A relative to the stationary point
kC = mass transfer coefficient in m
s
kgmolA
C L1 = the bulk fluid concentration in
m3
C Li = the concentration in the fluid next to the surface of the solid

Molecular Diffusion in Gases

A. Equimolar Counter diffusion in Gases

Figure 1
PA1 PA2
PB1 PB2

* *
JA JB

A diagram of 2 gases A and B at P=k in two large chambers connected by a tube where
molecular diffusion at steady state is occurring.
 P
PA1 PB2

Figure 2

PB1 PA2

Equimolar Counter Diffusion of gases A and B

Stirring in each chamber keeps the concentration in each chamber uniform.

The partial pressure

PA1  PA2 PB2  PB1

Molecules of A diffuse to the right and molecules of B to the left,

Since the total pressure P is constant throughout, the net mole of A diffusing to the right
must equal to the net mole of B to the left.

If this is not so, the total P would not remain constant. This means
* *
J Az =  J Bz

The subscript z is dropped when the direction is obvious.

Writing Fick’s Law for B for constant C

dCB
J B   DBA 
*

dz

Since P  PA  PB = constant, then

C  C A  CB dC  0

Differentiating both sides: 0  dC A  dCB

dC A  dCB Equation 1

  J B  DBA  B
dC A dC
J A   DAB 
* *
Equation 2
dz dz
Substitute eq. 1 in eq. 2 and canceling like terms

DAB  DBA
 This shows that for, a binary mixture of A and B, DAB for A diffusing into B is the same
as DBA for B diffusing into A.

Example 2: Equimolar Counter Diffusion

Ammonia gas (A) is diffusing through a uniform tube 0.1m long containing N2 gas (B) at
1.0132 105 Pa pressure and 298K . The diagram is similar to figure 1 and figure 2
At point 1: At point 2:

PA1  1.013 104 Pa PA2  0.507 104 Pa

m2 4
The diffusivity DAB  0.23 10
s
*
a. Calculate the flux J A at steady state

*
b. Repeat for J B

Solution:

z2  z1  0.1m ; T  298K

P  1.0132 105 Pa

JA 
* 
DAB PA1  PA2   0.23 10 1.013 10
4 4
 0.5070 104 
RT z2  z1  83142980.1  0

J A  4.7 107 kgmolA

*
m2  s

PB1  P  PA1

PB2  P  PA2

JB 
* 
DAB PB1  PB2 
RT z2  z1 

J B  4.7 107 kgmolB

*
m2  s
*
The (-) value for J B means the flux goes from point 2 to point 1
 B. General Case for Diffusion of Gases A and B Plus Convection
*
J A = diffusion flux of A relative to the moving fluid

N A = total flux of A relative to the stationary point

The velocity of A relative to the stationary point is the sum of the diffusion velocity and
the average or convective velocity

 A   Ad  M Equation 1

where:

 A is the velocity of A relative to a stationary pt.?

Expressed pictorially
A

M

Multiplying both side by C A

C A A  C A Ad  C AM Equation 2

Each of the 3 terms represent a flux

1st: C A A  N A
kgmolA
m2  s

total flux of A relative to the

stationary point

2nd: C A Ad  J A  the diffusion flux relative to the moving fluid

*

3rd: C AM  convective flux of A relative to the stationary point

eq. 2 becomes;

N A  J A  C AM
*
Equation 3

Let N = the total convective flux of the whole stream relative to the stationary point, then

N  CM  N A  N B Equation 4

N A  NB
Solve for  M  Equation 5
C
Substitute eq. 5 in eq. 3:

NA  JA *
CA
N A  N B  Equation 6
C
*
Since J A is Fick’s Law in eq. 1

N A  CDAB
dX A C A
 N A  N B  Equation 7
dz C

This is the final general equation for diffusion plus convection to use when the flux N A is
used, which is relative to a stationary point.

A similar equation can be written for N B :

N B  CDBA 
dX B CB
 N A  N B  Equation 8
dz C

C. Special Case for a Diffusion through stagnant, Non-diffusing B

To derive the case for A diffusing in stagnant. Non-diffusing B, N B  0 is

substituted in eq. 7

N A  CDAB 
dX A C A
 N A  0 Equation 9
dz C
The convective flux of A is

CA
N A  0
C

keeping the PT constant, substituting

P PA
C , PA  X A P , P
RT XA

PA dPA P C
C ; CdX A  and X A  A  A
RTX A RT P C

 DAB dPA PA
NA     NA Equation 10
RT dz P
CdX A XA
Rearranging and integrating,

 P   DAB dPA
N A 1  A   
 P RT dz
PA2
 DAB
z2
dPA
N A  dz   Equation 11
z1
RT P
PA1 1  A
P

DAB  P 1  X A2
NA  ln
RT z2  z1 
Equation 12
1  X A1

Since P  PA1  PB1  PA2  PB2

PB1  P  PA1 ; PB2  P  PA2

A log mean of the inert B is

PB2  PB1 PA  PA1

PBM   2
P P  PA2 Equation 13
ln B2 ln
PB1 P  PA1

substitute eq. 13 in eq. 12

DAB  P
NA 
RT z2  z1   PBM

PA1  PA2  Equation 14

Example 3: Diffusion of Water Through Stagnant, Non-diffusing Air

Water in the bottom of a narrow metal tube is held at constant T of 293K. The total P of
air (assumed) dry is 1.01325 105 Pa (1atm) and the temperature is 293K(20°C). Water
evaporates and diffuses through the air in the tube, and the diffusion path z2  z1 is 0.1524m
(0.5ft) long. Calculate the rate of evaporation at steady state in lbmol and kgmole . The
hr  ft 2 m2  s
diffusivity of water vapor at 293K and 1atm pressure is 0.25 104 m2 . Assume that the system
s
is isothermal. Use SI and English units.

Solution:

m2 ft 2
1st: Convert DAB from to
s hr
2
DAB  0.969 ft
hr
From the handbook:

Vapor Pressure of H2O at 20°C = 17.54mm

17.54
or PA1   0.0231atm  2.341103 Pa
760

PA2  0 (pure air); PB2  1

T  20C = 68F = 528R = 298K

3
R  0.73 ft atm
lbmol R

2nd: Calculate PBM = log mean value of inert B

use eq. 13

PB2  PB1 1  0.9769 0.0231

P'BM 
P
ln  B2

 ln

10.9769


0.0234
 PB1 

P'BM  0.988atm = 1.001105 Pa

Since PB1 is close to PB2 , the linear mean

PB1  PB2  could be used and would be very close
2
to PBM .

z2  z1  0.5

use eq. 14

0.96910.0231  0
NA 
DAB P
RT z2  z1   PBM

 PA1  PA2  
0.735280.50.988

lb mol
N A  1.175 104
hr  ft 2

kgmol
N A  1.595 107
s  m2
D. Diffusion Through A Varying Cross-Sectional Area

N
NA  A Equation 15
A
where:

N A is (kg mols A diffusion)/sec

At steady state N A will be constant but not A for varying area

Case 1: Diffusion from a sphere

To illustrate use eq. 15

Let us consider diffusion to or from a sphere in a gas


NA
NA  Equation 16
4  r 2
This is the case of A diffusing through stagnant, non-diffusing B

Use eq.16 and equate to eq. 11


NA  DAB dPA
NA  =  Equation 17
4  r 2
RT  PA 
1  dr
 P

Note that dr was substituted for dz . Rearranging and integrating between r1 and some
point r2 a large distance away

 PA2
N A 2 dr  DAB
r
dPA
4 r1 r 2 
 Equation 18
RT P 
PA1
1  A dr
 P

N A  1 1  DAB P P  PA2
     ln Equation 19
4  r1 r 2  RT P  PA

1
Since r2  r1 , 0
r2

Substitute PBM from eq. 13 to eq. 19

 
NA D P PA  PA2
 N A1  AB  1 Equation 20
4  r12 RTr1 PBM

This equation can be simplified further. If PA , is small compared to P (a dilute gas phase),
PA1
PBM  P . Also, setting 2r1  D1 , diameter and C A1  , we obtain
RT

N A1 
2 DAB
D1

C A1  C A2  Equation 21

This equation can be used for liquids, where

DAB is the diffusivity of A in the liquid

Example 4: Evaporation of a Naphthalene Sphere

A sphere of naphthalene having a radius of 2mm is suspended in a large volume of

still air at 318K and 1.01325x105Pa (1atm). The surface temperature of the naphthalene
can be assumed to be at 318K and its VP at 318K is 0.555mmHg. The DAB of
naphthalene in air at 318K is 6.92x10-6 m2/s. Calculate the rate of evaporation of
naphthalene from the surface.

Solution:

2
DAB  6.92 106 m
s

 0.555 
PA1   1.01325 10  74 Pa
5

 760 

2
PA2  0 , r1  m
1000
3
R  8314 m Pa
kgmol  K
 PB1  P  PA1  1.01325 105  74  1.01251105 Pa

PB2  P  PA2  1.01325 105  0  1.01325 105 Pa

Since the values of PB1 and PB2 are close to each other

PB1  PB2
PBM   1.0129 105 Pa
2
Substitute in eq. 20


DAB P PA1  PA2   6.92 10 1.01325 10 74  0
6 5

83143182 1.0129 10 

N A1  5
RTr1 PBM
1000

N A1  9.68 108 kgmolA

s  m2

Case 2: Diffusion through a Conduit of Non-uniform cross-sectional area

r2

r1
NA

pt.1
pt.2

In the figure, component A is diffusing at steady state through a circular conduit which is
tapered uniformly as shown. At point 1, radius is r1 and at point 2, radius r2. At position z in
the conduit, for A diffusing through stagnant, non-diffusing B.

Solution:

N  DAB dPA
N A  A2  
r RT  PA 
1  dz
 P

As shown, the variable radius r can be related to position z in the path as follows

 r r 
r   2 1  z  r1
 z2  z1 
The value of r is substituted
 PA2
 DAB
z2
NA dz dPA

 z1  r  r  
2

RT  P
PA1 1  A
Equation 22

   z  r1 
2 1
P
 z2  z1  

E. Equations for Diffusion in liquids

Since molecules in liquid are packed together much more closely than in gases, the
density and the resistance to diffusion in a liquid are much greater. Because of this
closer spacing of the molecules, the attractive forces between molecules play an
important role in diffusion.

Since the kinetic theory of liquids is only partially developed, we write the equation
for diffusion in liquids similar to those for gases.

In diffusion in liquids, an important difference from diffusion in gases is that the

diffusivities are often quite dependent on the concentration of the diffusivity components.

Case 1: Equimolar Counter Diffusion

N A  NB

NA 

DAB C A1  C A2 
z2  z1

NA 

DAB Cav X A1  X A2  Equation 23
z2  z1

where:

kgmolA
N A is the flux of A in
s  m2
m2
DAB the diffusivity if A in B in
s
kgmolA
C A1 the concentration of A in at point 1
m3
kgmolA
C A2 the concentration of A in at point 2
m3
X A1 the mole fraction of A at point 1 and Cavg define by
  1  2 
  
    M 1 M 2 
Cavg     Equation 24
 M  avg 2

where:

kgmol
Cavg is the average total concentration of A+B in
m3
kgmass
M 1 the average MW of the solution at point 1 in
kgmol
kg
1 the average density of the solution in at point 1
m3

Eq. 23 uses the average value of DAB which may vary some with concentration and the
average value of C , which may be vary with concentration. Usually, the linear average of C
is used as in eq. 24. Equimolar counter-diffusion only occurs very infrequently in liquids.

Case 2: Diffusion of A through non-diffusing B

The most important case of diffusion in liquid is that where solute A is diffusing
and solvent B is stagnant or non-diffusing.

An example is a dilute solution if propionic acid (A) in a water (B) solution being
contacted with toluene.

Only the propionic acid (A) diffuses thru’ the water phase, to the boundary, and
then into the toluene phase.

The toluene-water interface is a barrier to diffusion of B & N B  0 . If eq. 14 is

rewritten in term of concentrations by substituting,

P
C av  ; C A1 
PA1
; X BM 
PBM
RT RT P
We obtain equation for liquids at steady state

NA 
DAB Cavg
z2  z1 X BM
X A1  X A2  Equation 25

where:

X B2  X B1
X BM 
X 
ln  B 2 
 X B1 

Note that: X A1  X B1  X A2  X B 2  1.0

 For dilute solutions X BM is close to 1.0 and C is essentially constant, then eq. 25 is
simplified to

NA 

DAB C A1  C A2 
z2  z1

Example: Diffusion of Ethanol (A) through water (B)

An ethanol (A) -water (B) solution in the form of a stagnant film 2.0mm thick at 293K is
in contact at one surface with an organic solvent which ethanol is soluble and water is
insoluble.

Hence, N B  0 . At point 1, the concentration of ethanol is 16.8 wt % and the solution

density is 1  972.8
kg . At point 2, the concentration of ethanol is 6.8 wt. % and
m3
 2  988.1 kg
2
3 . The diffusivity of ethanol is 0.74 109 m . Calculate the steady-state
m sec
flux N A .

Solution:
2
DAB  0.74 109 m
s

M A  46.05

M B  18.02

For a wt. % of 6.8, mole fraction of ethanol (A) when using 100kg of solution is

6.8
X A2  46.05  0.0277
6.8  93.2
46.05 18.02

X B2  1  0.0272  0.9728

X A1  0.0732 ; X B1  0.9268

M 2   X 2M 2

To calculate M 2 at point 2:

100kg
M2   18.75 kg
0.1477  5.17kgmol kgmol
Similarly, M1  X M 1 1  X A1 M A1  X A2 M A2

M 1  20.07 kg
kgmol

Use eq.24

 1  2   972.8 988.1 
     
 M 1 M 2   20.07 18.75 
Cavg  
2 2

Cavg  50.6 kgmol

m3
X B1  X B2 0.9268  0.9723
To calculate X BM using 
2 2
The linear mean because their values are close to each other

X BM  0.949

Substitute to eq. 25

NA 
DAB C AV

X X
z2  z1  X BM A1 A2


NA 
0.74 10 50.60.0732  0.0277
9

 2 
 0.949
 1000 

N A  8.99 107 kgmol

s  m2
8.2 Diffusion Coefficient

Exam 1: Diffusion in a non-uniform cross-sectional area

The gas ammonia (A) is diffusing at steady state through N2 (B) by equimolar counter-
diffusion in a conduit 1.22m long at 25°C and a PT=101.32kPa abs. The PP of ammonia at
the left end is 25.33 kPa and at the other end 5.066kPa. The cross section of the conduit is
in the shape of an equilateral triangle being 0.061m at the left end and tapering uniformly to
2
0.0305m at the right end. Calculate the molar flux of ammonia DAB  0.23 104 m .
sec
Given:

s s
h h s tan 60
tan 60  ; h
60°C
s 2
2
s
h  0.866s

A
1
s 0.866s 
2

A  0.433s 2

NH 3  A to N 2 B 
2
DAB  0.23 104 m
sec
PT  101.32kPa
T  25C
PA  25.33kPa ;
1
PA2  5.066kPa
Required:

Molar flux NH3

Solution:

use eq. 22

NA  DAB dPA
NA   
0.433s 2
RT  PA 
1  dz
 P


 
z
N A 2 dz DAB P

0.433 z1 s 2

RT z2  z1 PBM
PA1  PA2

PB1  75.99kPa  0.75atm

PB2  96.254kPa  0.95atm

PB2  PB1 0.95  0.75

PBM 
ln
PB2

ln 0.95 
0.75

 0.846atm

PB1

dz

0.0305
0.061

1.22

0.061  s 0.061  0.0305


z 1.2

s  0.061  0.025z


1.22 0.2310 4 m2 125101
.33  5.066

 0.061  0.025z 
NA 2 s .325
0.433 0
dz 
0.08205 L  atm molK 298K 1.220.846

NA
655.738  1.822 107 kgmol m2  s
0.433

N A  1.2 1010 kgmol
sec m 2
Example 2: Diffusion of A through Stagnant B in a liquid

The solute HCl (A) is diffusing through a thin film of water (B) 2.0mm thick at 283K. The
concentration of HCl at point 1 at one boundary of the film is 12 wt. % HCl (density,
1  1060.7 kg ), and at the other boundary at point 2 it is 6 wt. % HCl
m3
(  2  1030.3
kg ). The diffusion coefficient of HCl in water is 2.5 109 m 2 . Assuming
m3 s
steady state and one boundary impermeable to water, calculate the flux of HCl in
kgmol .
s  m2
Solution:

use eq. 25  N A 
DAB

Cavg
X X
z2  z1  X BM A1 A2
 

NA 
2 DAB
D1

C A1  C A2 

C A1  1060.7 kg 3  0.12 kgHCl 1 kmol  3.4849 kmol

m kgsol' n 36.5kg m3

C A2  1030.3 kg  0.06 kgHCl 1 kmol  1.6936 kmol

m3 kgsol' n 36.5kg m3
Note:

For dilute solutions

X BM  1

CT  3.4849  1.6936  5.1785

3.4849
X A1   0.673
5.1785

1.6936
X A2   0.327
5.1785

N A  5.1785 kmol
m32.510 9 m2   0.327  0.673 
s  0.002 

N A  2.2397 106 kmol

s  m2