EKC 217:

MASS TRANSFER
1

TOPIC 1: DIFFUSION

COURSE OUTCOME
2

CO1: Perform calculations on diffusion and mass transfer problems.

Course Strategies:
Lectures covering:
Laws on diffusion and their applications as related to
mass transfer in practical applications such as diffusion
with bulk flow and through stagnant media.
The use of dimensionless co-relations of Sherwood
number with Reynolds Number and Schmidt Number.

Course Activities:
Lectures; in-class examples; tutorials and assignments
EKC 217: Introduction to Mass Transfer and Diffusion

Course Learning Objectives

3

By end of this topic, student should be able to:

1) Understand the concepts of mass transfer and
diffusion.
2) Carry out calculations on diffusion and mass
transfer problems.

EKC 217: Introduction to Mass Transfer and Diffusion

What is MASS TRANSFER?

4

A term used to indicate the transference/movement of a

component (at molecular level) in a mixture from a region
where its concentration is high to a region where the
concentration is lower.
Among some of the familiar phenomena that involves mass
transfer are:
1) Liquid in an open pail
evaporates into still air
because of the difference
in concentration of water
vapor at the water surface
and the surrounding air.
Liquid to gas
EKC 217: Introduction to Mass Transfer and Diffusion

2) A piece of sugar added

into a cup of coffee
eventually dissolves by
itself and diffuses to the
surrounding solutions.
Solid to liquid

3) A piece of solid CO2

(dry ice) also gets smaller
and smaller in time as the
CO2 molecules diffuse
into the air.
Solid to gas
EKC 217: Introduction to Mass Transfer and Diffusion

Mass transfer occurs by two basic mechanisms:

Molecular diffusion - random and spontaneous
microscopic movement of individual molecules in a gas,
liquid or solid.
Eddy (turbulent) diffusion due to turbulent flow of fluid.
In a binary mixture, molecular diffusion occurs because of
one or more different potentials or driving force, including
differences (gradients) of concentration, pressure (pressure
diffusion), temperature (thermal diffusion) and external force
fields (forced diffusion).
This chapter will only focus on molecular diffusion caused by
CONCENTRATION GRADIENTS as it is the most common
type of molecular diffusion in commercial separation process.
EKC 217: Introduction to Mass Transfer and Diffusion

The rate at which the process takes place is dependent both on

the driving force (concentration difference) and on the mass
transfer resistance.
In most of these applications, mass transfer takes place across
a phase boundary where the concentrations on either side of the
interface are related by the phase equilibrium relationship.
Where a chemical reaction takes place during the course of
the mass transfer process, the overall transfer rate depends on
both the chemical kinetics of the reaction and the mass transfer
resistance.

EKC 217: Introduction to Mass Transfer and Diffusion

Classification of Mass Transfer Operations

8

Based on the three various phases available,

i.e.: solid, liquid and gas, six possibilities of
contact are available:
1.
2.
3.
4.
5.
6.

Gas-Gas
Gas-Liquid
Gas-Solid
Liquid-Liquid
Liquid-Solid
Solid-Solid

EKC 217: Introduction to Mass Transfer and Diffusion

1) Gas-Gas
The phase contact between gas-gas is not practically
realized as most gasses are completely soluble in each
other.

2) Gas-Liquid
This is on of the most common phase contact in the
industries.
Among some of the industrial process that has this two
phase contact are distillation, absorption,
desorption/stripping.

EKC 217: Introduction to Mass Transfer and Diffusion

a) Distillation
The main function is to separate a
liquid mixture, of miscible and
volatile substances into individual
components by vaporization;
Utilizes the differences in volatility
for separation while the vapor phase
is created from the liquid by
application of heat;
Example of industrial process:
Separation of a mixture of alcohol
and water into its component and
the separation of a mixture of
benzene and toluene into its
component (Figure 1).
EKC 217: Introduction to Mass Transfer and Diffusion

10

Benzene

Mixture of
benzene &
toluene

Toluene

Figure 1

b) Gas Absorption
In gas absorption, a soluble vapor
is absorbed by means of a liquid in
which the solute gas is more or less
soluble using selective absorbent.
For instance, if a mixture of air
and ammonia is in contact with
liquid water, a large portion of
ammonia but essentially no air will
dissolve in the liquid
(Figure 2).
Through this, the air/ammonia
mixture can be separated.
The process need more than one
column in order to achieve 100%
separation.
EKC 217: Introduction to Mass Transfer and Diffusion

11

Air (outlet)

Water (inlet)

Absorption
column

Air & ammonia Water & ammonia

(inlet)
(outlet)

Figure 2

c) Gas Desorption/Stripping
Similar to gas absorption, but the only difference is purely
in the direction of solute transfer;
For example, if air is brought into contact with an
ammonia-water solution, some of the ammonia will leave
the liquid phase and enters the gas phase.
3) Gas-Solid
If a solid is moistened with a volatile liquid and is exposed
to a relatively dry gas, the liquid leaves the solid and
diffuses into the gas, an operation generally known as
DRYING.

EKC 217: Introduction to Mass Transfer and Diffusion

12

4) Liquid-Liquid
Separations involving the contact of two insoluble
liquid phase are known as liquid-liquid extraction.
A simple and familiar example is the separation of acetone
from acetone-water solution using carbon tetrachloride. If the
acetone-water solution is shaken in a separatory funnel with
carbon tetrachloride and the liquids are allowed to settle, a
large portion of the acetone will be found in the carbon
tetrachloride-rich phase and will thus have been separated
from the water.
Water

Acetone-water
solution

Carbon
tetrachloride-acetone
solution

Carbon tetrachloride
solution

EKC 217: Introduction to Mass Transfer and Diffusion

13

5) Liquid-Solid
Crystallization is one of the process that involves liquid and solid
phase. It is used to obtain materials in attractive and uniform
crystals of good purity, separating a solute from the melt or a
solution and leaving impurities behind .
Leaching is a process whereby liquid solvent is used to dilute
selective component in a solid mixture. For example, the leaching of
gold from its ore by cyanide solution and cotton seed oil from the
seeds by hexane.
6) Solid-Solid
E.g.: diffusion of carbon into iron during
case-hardening, doping of semiconductors for transistors, migration
of doped molecules in semiconductors
at high temperature.
EKC 217: Introduction to Mass Transfer and Diffusion

14

DIFFUSION
15

Diffusion involves movement of a component (at molecular level) in a

mixture from a region where its concentration is high to a region

where the concentration is lower.
The rate of diffusion is conveniently described in terms of a molar
flux (mole per unit area per unit time), the area being measured in a
direction normal to the diffusion.
In a binary mixture, molecular diffusion occurs because of one or
more different potentials or driving force, including differences
(gradients) of concentration, pressure (pressure diffusion),
temperature (thermal diffusion) and external force fields (forced
diffusion).
We will only focus on molecular diffusion caused by concentration
gradients as it is the most common type of molecular diffusion in
commercial separation process.
EKC 217: Introduction to Mass Transfer and Diffusion

In all mass transfer operations, diffusion occurs in at least one

phase and often in both phases.

For example, in gas absorption, solute diffuses through the gas
phase to the interface between the phases and through the liquid
phase from the interface.

GAS

LIQUID

This chapter is only restricted to binary mixture and steady state

is assumed.
EKC 217: Introduction to Mass Transfer and Diffusion

16

MOLECULAR DIFFUSION

A container is filled
with dye solution

Clear water is added

on top, dye solution is
undisturbed

Uniform mixture of dye

and water is formed

Water molecules
Dye molecules
EKC 217: Introduction to Mass Transfer and Diffusion

Water and dye

molecules move
across the
horizontal plane

17

A container is filled with dye solution.

Clear water is then carefully added on top, so that the dye

solution on the bottom is undisturbed.

At the first instance, a sharp boundary between the two
layers. However, after a short while, the upper layer
becomes colored and the lower layer becomes less colored.
The color change process is through diffusion of the dye
molecules.
By taking the horizontal plane across the solution, on the
average, a fraction of molecules in the solution below the
plane will cross over to the region above, and the same
fraction will cross in the opposite direction.

EKC 217: Introduction to Mass Transfer and Diffusion

18

Since the concentration of dye molecules is higher in

the lower region than the upper, there will be a net rate
of mass transfer of dye molecules will take place from
the lower region to the upper region.
After a longer period, the concentration of dye will be
uniform throughout the solution.

EKC 217: Introduction to Mass Transfer and Diffusion

19

Based on these observations, we can conclude that:

Mass transfer by ordinary molecular diffusion occurs

because of a concentration difference or gradient,
i.e.: a species diffuses in the direction of decreasing
concentration.
The mass transfer rate is proportional to the area
normal to the direction of mass transfer and not the
volume of the mixture. Therefore, the rate of
diffusion can be expressed as a FLUX.
Mass transfer stops when the concentration is
uniform.

These observations were then quantified by Fick in

1855, and it is known as FICKS LAW.

EKC 217: Introduction to Mass Transfer and Diffusion

20

FICKS LAW
21

Ficks Law for steady state diffusion of a binary mixture of

may be written as:

J A DAB

dc A
dz

(for component A)

A and B
------ (1.1)

where:

JA
DAB
cA
z

= molar flux of component A in the z direction due to

molecular diffusion (mole per unit area per unit time,
mole A/m2.s)
= Diffusivity/Diffusion coefficient of molecule A in B (m2/s)
= Concentration of component A (mole per unit volume,
mole A/m3)
= Distance in the direction of diffusion (m)

EKC 217: Introduction to Mass Transfer and Diffusion

Similarly, for component B :

dcB (for component B)

------ (1.2)
J B DBA
dz
Ficks Law for steady state diffusion of a binary mixture of A
and B may also be written in many other ways, such as:
1) Gradients of mole fraction:

J A cDAB

------ (1.3)

dx A
dz

where:
c = Total molar concentration of component A and B
xA = Molar fraction of component A
NOTE: cxA = cA
EKC 217: Introduction to Mass Transfer and Diffusion

22

2) In term of partial pressure:

cA

(since yA = pA/pT)

p A p A pT
p

yA T
RT pT RT
RT

where:
pA = partial pressure of A
pT = total pressure of the system
Therefore:

J A DAB

dc A
p dy
DAB T A
dz
RT dz

EKC 217: Introduction to Mass Transfer and Diffusion

23

------ (1.4)

REVIEW:
Different expressions of the concentrations in a binary mixtures of component
A and B.

EKC 217: Introduction to Mass Transfer and Diffusion

24

Exercise:
The composition of air is often given in terms of only the two
principal species in the gas mixture:
Oxygen, O2
Nitrogen, N2

yO2 = 0.21
yN2 = 0.79

Determine the mass fraction of both oxygen and nitrogen and

the mean molecular weight of the air when it is maintained at
25C (298 K) and 1 atm (1.013 x 105 Pa). The molecular weight of
oxygen is 0.032 kg/mol and of nitrogen is 0.028 kg/mol.
[Ans: O2 = 0.23, N2 = 0.77,
mean molecular weight of mixture = 0.0288 kg/mol]
EKC 217: Introduction to Mass Transfer and Diffusion

25

Example 1: Molecular diffusion of He in N2

A mixture of He and N2 gas is26contained in a pipe at 298 K
and 1 atm total pressure, which is constant throughout. At
one end of the pipe at point 1 the partial pressure, pA1 of He
is 0.6 atm and the other end 0.2 m pA2 = 0.20 atm. Calculate
the flux of He at steady state if DAB of the He-N2 is 0.687 x
10-4 m2/s. The universal gas constant, R is given as 82.057
cm3.atm/gmol.K
Solution:
Beginning from the Ficks Law:

J He DHeN 2

dcHe
dz

EKC 217: Introduction to Mass Transfer and Diffusion

26

Rearranging Eq. (1.1) and integrating:

z2

cHe 2

z1

cHe1

J He dz DHeN 2

J He

dcHe

DHeN 2 cHe1 cHe 2

z2 z1

From the perfect gas law, pHeV = nHeRT, thus:

pHe1 nHe
cHe1

RT
V

EKC 217: Introduction to Mass Transfer and Diffusion

27

Substituting into the earlier equation:

J He

DHeN 2 pHe1 pHe 2

RT ( z2 z1 )

Putting in all the known values:

J He

(0.687 x 10 4 )(0.6 0.2)

(82.06 x 10-3 )(298)(0.2 0)

5.63 x 10-6 kgmole He/m 2 s

EKC 217: Introduction to Mass Transfer and Diffusion

28

Correlation between Diffusivity

29

For diffusion of A and B in a gas at constant temperature and

pressure:

P
c A cB c
RT

------ (1.5)

The relationship between DAB and DBA is easily determined

for ideal gases, since the molar density (concentration) does not
depend on the composition:

dcA dcB dc 0
EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.6)

Choosing the reference plane for which there is zero volume

flow, the sum of the molar diffusion fluxes of A and B can be
set to zero:

J Az J Bz 0

------ (1.7)

The subscript z is often dropped when the direction is obvious.

Writing Ficks Law for A and B for constant total
concentration, c :

dc A
J A DAB
dz

and

dcB
J B DBA
dz

EKC 217: Introduction to Mass Transfer and Diffusion

30

------ (1.8)

Replacing Eq. (1.8) into (1.7):

DAB

dc A
dcB
DBA
0
dz
dz

------ (1.9)

Since dcA = -dcB , therefore:

DAB DBA

EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.10)

31

Diffusion process together with convection

32

Up to now, we have considered Ficks Law for diffusion in a

stationary fluid; i.e.: there has been no net movement or
convection flow of the entire phase of the binary mixture A and
B.
Many practical problems such as the
evaporation of water from a lake
under the influence of the wind or
the mixing of two fluids as they flow
in a pipe, involve diffusion in moving
medium, i.e. bulk motion is cause by
the external force.
EKC 217: Introduction to Mass Transfer and Diffusion

What is CONVECTIVE MASS TRANSFER?

-Mass transfer between a moving fluid and a surface or between
immiscible moving fluids separated by a mobile interface (gas/liquid or
liquid/liquid contactor)
Mass transfer = diffusion + bulk motion of medium (convective)
The diffusion flux, JA occurred because of the concentration gradient. The
rate at which moles of A passed a fixed point to the right, which will be
taken as a positive flux, is JA kg mole A/m2s.
This flux can be converted to a velocity of diffusion of A to the right by:

m kg mole
J A (kg mole A/m 2 s) Ad c A

3
m
s

where Ad is the diffusion velocity of A in m/s.

EKC 217: Introduction to Mass Transfer and Diffusion

33

------ (1.11)

Now lets consider what happens when the whole fluid is moving in bulk
or convective flow to the right.
The molar average velocity of the whole fluid relative to a stationary
point is M (m/s). Component A is still diffusing to the right, but now
its diffusion velocity, Ad , is measured relative to the moving fluid.
To a stationary observer, A is moving faster than the bulk of the phase,
since its diffusion velocity, Ad , is added to that of the bulk phase, M .
Expressed mathematically, the velocity of A relative to the stationary
point is the sum of the diffusion velocity and the average or convective
velocity:
------ (1.12)
A Ad M

where A is the velocity of A relative to a stationary point.

EKC 217: Introduction to Mass Transfer and Diffusion

34

Expressed pictorially:
A
Ad

A = actual velocity of A
Ad = diffusional velocity of A
M = velocity of bulk

observer sees actual movement as A

Multiplying Eq. (1.12) by cA:

c A A c A Ad c AM

------ (1.13)

Each of the three terms represents a flux. The first term, cAA, can
be represented by the flux NA kg mole A/m2s. This is the total flux
of A relative to the stationary point. The second term is JA, the
diffusion flux relative to the moving fluid. The third term is the
convective flux of A relative to the stationary point.
EKC 217: Introduction to Mass Transfer and Diffusion

35

Hence, Eq. (1.13) becomes:

N A J A cAM

------ (1.14)

Let N be the total convective flux of the whole stream relative to the
stationary point. Then,

------ (1.15)

N cM N A N B
Solving for M (bulk velocity) gives:

N A NB
c

------ (1.16)

Substituting Eq. (1.16) into (1.14):

cA
N A J A (N A NB )
c
EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.17)

36

Since JA is Ficks law:

N A cDAB

dx A c A
(N A NB )
dz
c

------ (1.18)

Equation (1.18) is the final general equation for diffusion plus

convection to use when the flux NA is used, which is relative to the
stationary point. A similar equation can be written for NB:

N B cDBA

dxB cB
(N A NB )
dz
c

------ (1.19)

To solve Eq. (1.18) or (1.19), the relation between the flux NA and NB
must be known. Eq. (1.18) and (1.19) hold for diffusion in gas, liquid or
solid.

For equimolar counter diffusion, NA = -NB and the convective term in

Eq. (1.18) becomes zero. Then, NA = JA = -NB = -JB .
EKC 217: Introduction to Mass Transfer and Diffusion

37

Eq. (1.18) and (1.19) can also be used in different forms. For
example, since N = cM and cxA = cA, thus:

N A c A M DAB

dc A
dz

------ (1.20)

Therefore, the appropriate equation used to solve a problem

would entirely depends on the information given in the
problem.
Equation (1.18) or (1.20) is the basic equation for mass transfer
in a non-turbulent fluid phase. It accounts for the amount of
component A carried by the convective bulk flow of the fluid
and the amount of A being transferred by molecular diffusion.
EKC 217: Introduction to Mass Transfer and Diffusion

38

There are several types of situation covered by Eq. (1.18) or

(1.20).
Among two of them that will be discussed in the syllabus are:
1) Equimolar counterdiffusion

2) Unimolecular diffusion (diffusion of a single component

through stationary second component).

EKC 217: Introduction to Mass Transfer and Diffusion

39

Equimolar counterdiffusion
40

In equimolar counterdiffusion,
the molar fluxes of A and B is
equal, but in opposite direction
or the net volumetric and molar
flows are zero.
A typical example of this case is
the diffusion of A and B in the
vapor phase for distillation that
have constant molar overflow.

EKC 217: Introduction to Mass Transfer and Diffusion

Since the net volumetric and molar flows are zero, thus Eq.
(1.18) can be used with the convective term is set to zero, as
shown below:
------ (1.21)

dx A
J A cDAB
dz

Eq. (1.21) is then integrated over a film thickness of zT,

assuming a constant flux, JA:
xA

zT

DAB c dx A J A dz
x Ai

------ (1.22)

EKC 217: Introduction to Mass Transfer and Diffusion

41

Integrating Eq. (1.22) and rearranging gives:

DAB c
DAB
JA
( x Ai x A ) or J A
(c Ai c A )
zT
zT

------ (1.23)

The concentration gradient for A is linear in the film, and the

gradient for B has the same magnitude but the opposite sign.

EKC 217: Introduction to Mass Transfer and Diffusion

42

Example 2:
Ammonia gas (A) is diffusing through a uniform tube 0.10 m
long containing N2 gas (B) at 1.0132 x 105 Pa pressure and 298 K.
At a point 1, pA1 = 1.013 x 104 Pa and at a point 2, pA2 = 0.507 x 104
Pa. The diffusivity DAB = 0.230 x 10-4 m2/s. Calculate the flux JA
at steady state and repeat for JB.
Solution:
Given: P = 1.0132 x 105 Pa
z2 z1 = 0.10 m

T = 298 K

Substitute known values into the following equation:

DAB p A1 p A2
JA
RT ( z2 z1 )
EKC 217: Introduction to Mass Transfer and Diffusion

43

0.23 x 10 1.013 x 10

JA

0.507 x 10 4
8314(298)(0.10 0)
4

4.70 x 10-7 kgmole A/m2 s

For component B:
pB1 = P - pA1 = 1.0132 x 105 1.013 x 104 = 9.119 x 104 Pa
pB2 = P pA2 = 1.0132 x 105 0.507 x 104 = 9.625 x 104 Pa
Hence,

0.23 x 10 9.119 x 10

JB

9.625 x 10 4
8314(298)(0.10 0)
4

- 4.70 x 10-7 kgmole B/m 2 s

The negative value for JB means the flux goes from point 2 to point 1.

EKC 217: Introduction to Mass Transfer and Diffusion

44

Unimolecular Diffusion
45

In unimolecular diffusion,
mass transfer of
component A occurs
through stagnant
component B, NB = 0.
Therefore, the total flux to
or away from the interface,
N is the same as NA.

EKC 217: Introduction to Mass Transfer and Diffusion

A typical example of this case is the evaporation of a liquid

with the diffusion of the vapor from the interface into a gas
stream.
Based on the definition of unimolecular diffusion, Eq. (1.18)
becomes:

N A cDAB

dx A
xA N A
dz

EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.24)

46

Rearranging:
dx A
N A (1 x A ) cDAB
dz

NA
1
or
dz
dx
DAB c
1 xA

------ (1.25)

Integrating:
x A dx
N A zT
1 xA
dz
ln

x Ai 1 x
DAB c 0
1 x Ai
A

------ (1.26)

Or:

DAB c 1 x A
NA
ln
zT
1 x Ai

EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.27)

47

MOLECULAR DIFFUSION IN GASES

48

Special case for A diffusing through stagnant B:

In the gas phase,
e.g.: if ammonia (A)
were being absorbed from
air (B) into water, only
ammonia diffuses since air
does not dissolve
appreciably in water.

EKC 217: Introduction to Mass Transfer and Diffusion

Thus, NB = 0 and NA = constant.

From Eq. (1.18):
N A cDAB

dx A c A
(N A NB )
dz
c

------ (1.28)

Since NB = 0, therefore:
N A cDAB

dx A c A
(N A )
dz
c

EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.29)

49

PT
c
,
RT

------ (1.30)

p A x A PT

Hence:
DAB dp A p A
NA

NA
RT dz PT

------ (1.31)

Rearranging:
pA
DAB dp A

N A 1

RT dz
PT

------ (1.32)

Integrating:

NA

z2

z1

DAB p A 2 dp A
dz
RT p A1 1 p A / PT

EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.33)
50

After integration, Eq. (1.33) becomes:

DAB PT
PT p A2
NA
ln
RT ( z2 z1 ) PT p A1

------ (1.34)

Since:
PT pA2 = pB2 ,
PT pA1 = pB1 ,
pB2 pB1 = pA1 pA2 , then:

DAB PT
p A1 p A2
pB 2
NA
ln
RT ( z2 z1 ) pB 2 pB1
pB1

------ (1.35)

The logarithmic mean of pB1 and pB2 is given by:

pBM

pB 2 pB1

ln( pB 2 / pB1 )

EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.36)
51

Substituting Eq. (1.36) into Eq. (1.35) gives:

DAB PT
NA
( p A1 p A2 )
RT ( z2 z1 ) pBM

------ (1.37)

Compare with the earlier equation for equimolar counterdiffusion:

DAB p A1 p A2
JA
RT ( z2 z1 )

Therefore, in the present case, PT/pBM can be regarded as

correction factor.

EKC 217: Introduction to Mass Transfer and Diffusion

52

In addition, for gases, Eq. (1.14): N A J A c AM can also be

expressed using mole fraction in vapor phase (yA), since:

cA M y A

and

N
M
M

where:
M = molar density (kgmole/m3)
= 1/22.41 kgmole/m3 (at standard conditions, 0C & 1 atm)
yA = mole fraction of component A in vapor phase
N = total convective flux of the whole stream relative to
the stationary point (kgmole/m2s)
M = molar average velocity (ms-1)
cA = molar concentration of component A (kgmole/m3)
EKC 217: Introduction to Mass Transfer and Diffusion

53

Eq. (1.14) becomes:

dy A
N A y A N DAB M
dz

------ (1.38)

Since N = NA + NB , and when only component A is being

transferred (i.e.: NB = 0), the total flux to or away from the
interface N is the same as NA, then Eq. (1.38) becomes:

dy A
N A y A N A DAB M
dz

EKC 217: Introduction to Mass Transfer and Diffusion

54

------ (1.39)

Rearranging and integrating:

dy A
N A (1 y A ) DAB M
dz
z2

yA2

z1

y A1

N A dz DAB M

------ (1.40)

dy A
(1 y A )

DAB M 1 y A2
NA
ln
z2 z1 1 y A1

EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.41)

------ (1.42)

55

Similarly,

yB1 = 1 yA1
yB2 = 1 yA2
yB2 yB1 = yA1 yA2
Then,

DAB M y A1 y A2 yB 2
NA

ln
z2 z1 yB 2 yB1 yB1
The logarithmic mean of
yB1 and yB2 is given by:

yBM

yB 2 yB1

ln( yB 2 / yB1 )

------ (1.43)

------ (1.44)

Finally, by substituting Eq. (1.44) into Eq. (1.43) gives:

DAB M
NA
( y A1 y A2 )
( z2 z1 ) yBM
EKC 217: Introduction to Mass Transfer and Diffusion

56

------ (1.45)

Example 3:
Water in the bottom of a narrow metal
tube is held at a constant temperature of
293 K. The total pressure of air (assume
dry) is 1.01325 x 105 Pa (1.0 atm) and the
temperature is 293 K (20C). Water
evaporates and diffuses through the air in
the tube and the diffusion path z2 z1 is
0.1524 m (0.5 ft) long. The diagram is
similar to the shown figure. Calculate
the rate of evaporation at steady state in
lb mol/ft2 h and kgmole/m2 s. The
diffusivity of water vapor at 293 K and 1
atm pressure is 0.250 x 10-4 m2/s. Assume
that the system is isothermal. Use SI and
English units.
EKC 217: Introduction to Mass Transfer and Diffusion

57

pA2 = 0

Air (B)

0.5 ft

NA
pA1 = 0.0231 atm
Water (A)

T = 293 K

Solution:
The diffusivity is converted to ft2/h by using the conversion factor (refer
Appendix 1, McCabe, Smith and Harriott).

DAB (0.250 x 10-4 )(3.875 x 104 ) 0.969 ft 2 /h

Using Appendix 7 (McCabe, Smith and Harriott), the vapor pressure of
water at 20C (68 F) is 0.3402 lbf/in2 or 2345.6 N/m2.

2345.6
p A1
0.0231 atm
5
1.01325 x 10

and

p A2 0 (pure air)

T = 460 +68 = 528R = 293 K

R = 82.057 cm3 atm/gmole K = 0.730 ft3 atm/lbmole R

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58

To calculate the value of pBM (from Eq. 1.36):

pB1 = PT pA1 = 1.00 0.0231 = 0.9769 atm

pB2 = PT pA2 = 1.00 0 = 1.00 atm
Therefore:
pBM

pB 2 pB1
1.00 0.9769

0.988 atm 1.001 x 105 Pa

ln( pB 2 / pB1 ) ln(1.00 / 0.9769)

Since pB1 is close to pB2 , the linear mean (pB1 +pB2)/2 could be
used and would be very close to pBM .

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59

Substituting in Eq. (1.37) with z2 z1 = 0.5 ft (0.1524 m), thus:

NA

DAB PT
( p A1 p A 2 )
RT ( z 2 z1 ) pBM
0.969(1.0)(0.0231 0)
0.730(528)(0.5)(0.988)

1.175 x 10 4 lbmole/ft 2 h

NA

DAB PT
( p A1 p A2 )
RT ( z2 z1 ) pBM

(0.250 x 10 4 )(1.01325 x 105 )(2.341 x 103 0)

8314(293)(0.1524)(1.001 x 105 )
1.595 x 10 7 kgmole/m 2 s

EKC 217: Introduction to Mass Transfer and Diffusion

60

Exercise:
a) For the diffusion of solute A through a layer of gas to an
absorbing liquid with yAi = 0.20 and yA = 0.10, calculate the
rate transfer for unimolecular diffusion compared to that for
equimolar counter diffusion.
b) What is the value of yA halfway through the layer for
unimolecular diffusion?
[Ans: yA = 0.1515]

EKC 217: Introduction to Mass Transfer and

Diffusion

61

MOLECULAR DIFFUSION IN LIQUIDS

62

Diffusion of solutes in liquid is very important in many

industrial processes especially in such separation operations
such as:
1) Gas absorption
2) Distillation
3) Liquid-liquid extraction or solvent extraction
Rate of molecular diffusion in liquids is considerably slower
than in gases.
The molecules in a liquid are very close together compared to
a gas. Therefore, the molecules of the diffusing solute A will
collide with molecules of liquid B more often and diffuse
more slowly than in gases.
EKC 217: Introduction to Mass Transfer and Diffusion

In diffusion in liquids, an important difference from diffusion

in gases is that the diffusivities are often dependent on the
concentration of the diffusing components.
Similar to those for gases, equations for diffusion in liquids
can be classified in two cases:
1) Steady-state equimolar counterdiffusion:
Starting from Eq. (1.18): N A cDAB dx A c A ( N A N B )
dz
c
and knowing NA = -NB , then:
DAB cav
DAB
JA
( x Ai x A )
(c Ai c A )
zT
zT

EKC 217: Introduction to Mass Transfer and Diffusion

63

------ (1.46)

cav is defined as follows:

cav

M av

1
2

M1 M 2

------ (1.47)

where:

cav
M1
1

= average total concentration of A + B (kgmole/m3)

= average molecular weight of the solution at point 1
(kg mass/kgmole)
= average density of the solution at point 1 (kg/m3)

EKC 217: Introduction to Mass Transfer and

Diffusion

64

2) Steady-state diffusion of A through non-diffusing B:

NA = constant, NB = 0

DAB
NA
( z2 z1 ) xBM
where:

( x A1 x A2 )
M av

xBM

------ (1.48)

xB 2 xB1
ln( xB 2 / xB1 )

Note that xA1 + xA2 = xB1 + xB2 = 1.0

For dilute solution, xBM is close to 1.0 and c is essentially constant.
Then, Eq. (1.48) simplifies to:

DAB
NA
(c A1 c A2 )
( z2 z1 )
EKC 217: Introduction to Mass Transfer and Diffusion

------ (1.49)
65

Example 4:
Calculate the rate of diffusion of acetic acid (A) across a film of
nondiffusing water (B) solution 1 mm thick at 17C when the
concentrations on opposite sides of the film are 9 and 3 wt %,
respectively. The diffusivity of acetic acid in the solution is
0.95 x 10-9 m2/s.
Solution:

Given:
(z2 z1) = 0.001 m
MA = 60.03 kg/kmole
MB = 18.02 kg/kmole
At 17 C: Density of the 9% solution = 1012 kg/m3
Density of the 3% solution = 1003.2 kg/m3
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66

Consider basis of solution = 1 kg,

At point 1:
x A1

0.09 / 60.03
0.0015

0.0288 mole fraction acetic acid

0.09 / 60.03 0.91 / 18.02 0.0520

xB1 1 0.0288 0.9712 mole fraction water

Molecular weight of the solution, M 1

1012

52.7 kmole/m 3
M 1 19.21

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67

1
19.21 kg/kmole
0.0520

Similarly, at point 2:
x A2

0.03 / 60.03
0.0005

0.0092 mole fraction acetic acid

0.03 / 60.03 0.97 / 18.02 0.0543

xB 2 1 0.0092 0.9908 mole fraction water

Molecular weight of the solution, M 2

1
18.42 kg/kmole
0.0543

1003.2

54.5 kmole/m 3
M2
18.42

Then,

M av

52.7 54.5
53.6 kmole/m 3
2

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68

xBM

xB 2 xB1
0.9908 0.9712

0.980
ln( xB 2 / xB1 ) ln(0.9908 / 0.9712)

Finally, substitute all known values in Eq. (1.48):

0.95 x 10 9
53.6(0.0288 0.0092)
NA
(0.001)(0.980)
1.018 x 10-6 kmole/m 2 s

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69