CP302 Separation Process Principles

Mass Transfer - Set 2

Prof. R. Shanthi

Example 6.2.2 from Ref. 1 (from Set 1)

Diffusion of water through stagnant, non-diffusing air:
Water in the bottom of a narrow metal tube is held at a constant
temperature of 293 K. The total pressure of air (assumed to be
dry) is 1 atm and the temperature is 293 K. Water evaporates
and diffuses through the air in the tube, and the diffusion path is
0.1524 m long. Calculate the rate of evaporation at steady state.
The diffusivity of water vapour at 1 atm and 293 K is 0.250 x 10-4
m2/s. Assume that the vapour pressure of water at 293 K is
0.0231 atm.
Answer: 1.595 x 10-7 kmol/m2.s

Prof. R. Shanthi

Solution: The set-up of Example 6.2.2 is shown in the figure.

Assuming steady state, equation (19) applies.
NA =

DAB P
(pA1 - pA2 )
RT(z2 z1) pB,LM

(19)

where
pB,LM =

Air (B)

(pA1 pA2 )
ln[(P - pA2 )/ (P - pA1 )]

z2 z1

Data provided are the following:

DAB = 0.250 x 10-4 m2/s;
P = 1 atm; T = 293 K;
z2 z1 = 0.1524 m;
pA1 = 0.0231 atm (saturated vapour pressure);

1
Water (A)

pA2 = 0 atm (water vapour is carried away by air at point 2)

Prof. R. Shanthi

Substituting the data provided in the equations given, we get

the following:
(0.0231 0 )
pB,LM =
ln[(1 - 0 )/ (1 0.0231 )]

NA =

= 0.988 atm

(0.250x10-4 m2/s)(1x1.01325x105 Pa) (0.0231 - 0) atm

(8314 J/kmol.K) (293 K) (0.1524 m) (0.988 atm)

= 1.595 x 10-7 kmol/m2.s

Prof. R. Shanthi

Example 6.2.3 from Ref. 1

Diffusion in a tube with change in
path length:
Diffusion of water vapour in a narrow
tube is occurring as in Example 6.2.2
under the same conditions. However,
as shown in the figure, at a given
time t, the level is z from the top. As
diffusion proceeds the level drops
slowly. Drive the equation for the
time tF for the level to drop from a
starting point z0 m at t = 0 to zF at t =
tF s as shown.

Prof. R. Shanthi

Air (B)

2
z
Z
zFF 0

1
Water (A)

Solution: Since the level drops

very slowly, we assume
pseudo-steady-state condition.
Therefore, equation (19)
applies in which (z2 z1) must
be replaced by z.
NA =

DAB P
RTz pB,LM

Air (B)

2
z
Z
zFF 0

(pA1 - pA2 )
z

(22)

1
Water (A)

Prof. R. Shanthi

Suppose that the level reduce by dz in dt time.

Mass balance yields the following:
(NA x A x dt) x MA = A x (A x dz)
where A is the cross-sectional
area of the tube, MA is the
molecular mass of water and
A is the density of water.

Air (B)

(23)

2
z
Z
zFF 0

1
dz

Water (A)

Prof. R. Shanthi

Combining equations (22) and (23), we get

MA DAB P (p - p ) dt
A dz =
A1
A2
RTz pB,LM

(24)

Rearranging (24), we get

zF

z dz =

tF

MA DAB P (p - p ) dt
A1
A2
RT pB,LM

z0

(zF2 z02)
A
=
2
tF =

Is it okay to take
pA1 and pA2 as
constants?

MA DAB P (p - p ) t
A1
A2
F
RT pB,LM
A RT pB,LM (zF2 z02)
2 MA DAB P (pA1 - pA2 )

(25)

This above equation is used to

Prof. R. Shanthi experimentally determine diffusivity DAB 8

Example 6.2.4 from Ref. 1

Evaporation of a Naphthalene sphere:
A sphere of naphthalene having a radius
of 2.0 mm is suspended in a large volume
of still air at 318 K and 1.01325 x 105 Pa
(1 atm). The surface temperature of the
naphthalene can be assumed to be at 318
K and its vapour pressure at 318 K is
0.555 mm Hg. The DAB of naphthalene in
air at 318 K is 6.92 x 10-6 m2/s. Calculate
the rate of evaporation of naphthalene
from the surface.
If the radius of the sphere decreases
slowly with time, drive the equation for the
time taken (tF) for the sphere to evaporate
completely.

Prof. R. Shanthi

pA2

dr

pA1

r1

Solution: All this time the mass transfer of A is taken as NA (in

moles/m2.s) and it is assumed to remain constant for systems at
steady-state or pseudo steady-state while carrying out the
integrations concerned. For the system considered here, we
cannot do that since the area across which the mass transfer
occurs vary as the radius changes.
p
A2

Therefore, we use the following definition:

Mass transfer
per area per
time

NA =

Mass transfer per time

nA
A

dr

(26)

pA1

Area of mass transfer

For the given system, equation (26) gives

nA
(27)
NA =
4r2
Prof. R. Shanthi

r1

10

Since the given system is a case of A diffusing through

stagnant, non-diffusing B, we could start from equation (15).
DAB dpA
pA (N + N )
A
B
NA = +
RT
dz
P
Setting NB = 0 and rearranging the above gives:
NA = -

DAB
RT

NA =

pA2

dpA
(1 - pA/P) dz

Using equation (26) and replacing dz by dr, the

above could be written as follows:
nA
=
2
4r

(15)

DAB
RT

dpA
(1 - pA/P) dr

dr

pA1

r1

which can be rearranged to give

Prof. R. Shanthi

11

nA
4

dr
r2

=-

DAB
RT

dpA
(1 - pA/P)

Integrating the above between r1 and some point r2

(which is a large distance away) gives the following:
nA
4

nA
4

r2

r1

1
r1

dr

=-

r2

1
r2

Prof. R. Shanthi

DAB
RT

pA2

pA2

dp

(1 - p /P)
A

pA1

DABP
RT

dr

pA1

P - pA2
P pA1

r1

(28)

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Since r2 >> r1, 1/ r2 is much smaller than 1/ r1 in equation (28),

and therefore neglected. So, equation (28) gives the following:
nA
=
4r1

DABP
RT

P - pA2
P pA1
pA2

Using equation (27) and the definition of pB,LM,

the above could be written as
NA =

nA
4r12

DABP
RTr1

pA1 - pA2
pB,LM

Equation (29) gives the rate of

evaporation of naphthalene from the
surface at r1 radius.

Prof. R. Shanthi

(29)

dr

pA1

r1

13

Data provided are the following:

DAB = 6.92 x 10-6 m2/s;
P = 1 atm;
T = 318 K;
r1 = 2 mm = 2/1000 m;
pA1 = 0.555/760 atm (saturated vapour pressure);
pA2 = 0 atm (no naphthalene vapour far away from the sphere)

Substituting the data provided, we get the following:

(0.555/760 0 )
pB,LM =
ln[(1 - 0 )/ (1 0.555/760 )]

NA =

= 0.9996 atm

(6.92x10-6 m2/s)(1.01325x105 Pa) (0.555/760 - 0) atm

(8314 J/kmol.K) (318 K) (2/1000 m) (0.9996 atm)

Prof. R. Shanthi

= 9.686 x 10-8 kmol/m2.s

14

Now, we need to drive the equation for the

time taken (tF) for the sphere to evaporate
completely. That is, the radius of the sphere is
r1 at t = 0 and it is zero at t = tF.
Since the radius of the sphere is said to
decrease slowly, we assume pseudo-steadystate condition. Therefore, equation (29)
applies in which r1 is replaced by as follows:
nA
NA = 42 =

DABP
RT

pA1 - pA2
pB,LM

(30)

pA2

pA1

d
r1

Sphere is enlarged.

Prof. R. Shanthi

15

Suppose that the surface reduce by d in dt

time. Mass balance yields the following:
(NA x A x dt) x MA = A x (A x (-d))

(31)

where A is the surface area of the sphere at

radius , MA is the molecular mass of the
sphere and A is the density of the sphere.

pA2

pA1

d
r1

Sphere is enlarged.

Prof. R. Shanthi

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Combining equations (30) and (31), we get

MA DAB P (p - p ) dt
- A d =
A1
A2
RT pB,LM
Rearranging and integrating, we get
0

- A d =

pA2

tF

MA DAB P (p - p ) dt
A1
A2
RT pB,LM

r1

Is it okay to assume that pA1 and pA2

remain constants as the radius of the
sphere () reduces from r1 to 0?

pA1

d
r1

Sphere is enlarged.

Prof. R. Shanthi

17

Integration gives the following results:

A

(r12 0)
=
2

tF =

MA DAB P (p - p ) t
A1
A2
F
RT pB,LM

A r12 RT pB,LM
2 MA DAB P (pA1 - pA2 )

The above gives the time taken for

the sphere to vanish completely at a
slow rate of evaporation.

(32)

pA2

pA1

d
r1

Sphere is enlarged.

Prof. R. Shanthi

18

Objectives of the slides that follow:

Estimating diffusivities

Prof. R. Shanthi

19

Estimating Diffusivity
Diffusivities for different systems could be estimated using
the empirical equations provided in the following slides as
well as those provided in other reference texts available in
the library and other sources.

Prof. R. Shanthi

20

Diffusivity of gases
An example at 1 atm and 298 K:
System

Diffusivity (cm2/s)

H2-NH3

0.783

H2-CH4

0.726

Ar-CH4

0.202

He-CH4

0.675

He-N2

0.687

Air-H2O

0.260

Air-C2H5OH

0.135

Air-benzene

0.0962

Prof. R. Shanthi

21

Binary Gas Diffusivity

DAB
P
Mi
T
Vi

- diffusivity in cm2/s
- absolute pressure in atm
- molecular weight
- temperature in K
- sum of the diffusion volume for component i

DAB is proportional to 1/P and T1.75

Prof. R. Shanthi

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Binary Gas Diffusivity

Prof. R. Shanthi

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Diffusivity in Liquids
For very large spherical molecules (A) of 1000 molecular
weight or greater diffusing in a liquid solvent (B) of small
molecules:

DAB =
DAB
T

VA

9.96 x 10-12 T
VA1/3

applicable for
biological
solutes such
as proteins

- diffusivity in cm2/s
- temperature in K
- viscosity of solution in kg/m s
- solute molar volume at its normal boiling point
in m3/kmol

DAB is proportional to 1/ and T

Prof. R. Shanthi

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Diffusivity in Liquids
For smaller molecules (A) diffusing in a dilute liquid solution of
solvent (B):

DAB =

1.173 x 10-12 ( MB)1/2 T

B VA0.6

applicable for
biological
solutes

DAB - diffusivity in cm2/s

MB - molecular weight of solvent B
T - temperature in K
- viscosity of solvent B in kg/m s
VA - solute molar volume at its normal boiling point in m 3/kmol
- association parameter of the solvent, which 2.6 for water,
1.9 for methanol, 1.5 for ethanol, and so on

DAB is proportional to 1/B and T

Prof. R. Shanthi

25

Diffusivity of Electrolytes in Liquids

For smaller molecules (A) diffusing in a dilute liquid solution of
solvent (B):

DoAB =

8.928 x 10-10 T (1/n+ + 1/n-)

(1/+ + 1/ -)

DoAB is diffusivity in cm2/s

n+ is the valence of cation
n- is the valence of anion
+ and - are the limiting ionic conductances in very dilute
solutions
T is 298.2 when using the above at 25oC

DAB is proportional to T
Prof. R. Shanthi

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Objectives of the slides that follow:

Mathematical modelling of steady-state

one dimensional diffusive mass transfer
in solids

Prof. R. Shanthi

27

Diffusion in solids
Diffusion in solids are occurring at a very slow rate.
However, mass transfer in solids are very important.
Examples:
Leaching of metal ores
Drying of timber, and foods
Diffusion and catalytic reaction in solid catalysts
Separation of fluids by membranes
Treatment of metal at high temperature by gases.

Prof. R. Shanthi

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Diffusion in solids
Diffusion in solids occur in two different ways:
- Diffusion following Ficks law (does not depend on
the structure of the solid)
- Diffusion in porous solids where the actual structure
and void channels are important

Prof. R. Shanthi

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Diffusion in solids following Ficks Law

Start with equation (13) from Set 1:
NA = -DAB

dCA
dz

CA (N + N )
+
A
B
CT

(13)

Bulk term is set to zero in solids

Therefore, the following equation will be used to describe
the process:
NA = -DAB

Prof. R. Shanthi

dCA
dz

(33)

30

Diffusion through a slab

Applying equation (33) for steady-state diffusion through a solid
slab, we get
NA = DAB (CA1 - CA2)
z2 - z1

(34)

where NA and DAB are taken as constants.

Drive (34) and compare it with
heat conduction equivalent.

CA1

CA2
z2-z1

Prof. R. Shanthi

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Relating the concentration and solubility

The solubility of a solute gas in a solid is usually expressed by
the notation S.
Unit used in general is the following:
m3 solute at STP
m3 solid . atm partial pressure of solute
Relationship between concentration and solubility:
S pA
CA =
kmol solute /m 3 solid
22.414
where pA is in atm
STP of 0oC and 1 atm

Prof. R. Shanthi

32

Relating the concentration and permeability

The permeability of a solute gas (A) in a solid is usually
expressed by the notation PM. in m3 solute at STP (0oC and 1
atm) diffusing per second per m2 cross-sectional area through a
solid 1 m thick under a pressure difference of 1 atm.
Unit used in general is the following:
m3 solute at STP . 1 m thick solid
s . m2 cross-sectional area . atm pressure difference
Relationship between concentration and permeability:
PM = DAB S
where DAB is in m2/s and S is in m3/m3.atm
Prof. R. Shanthi

33

Example 6.5.1 from Ref. 1

Diffusion of H2 through Neoprene membrane:
The gas hydrogen at 17oC and 0.010 atm partial pressure is
diffusing through a membrane on vulcanized neoprene rubber
0.5 mm thick. The pressure of H2 on the other side of 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 solid. atm and the diffusivity DAB is 1.03 x 10-10 m2/s at
17oC.
Answer: 4.69 x 10-12 kmol H2/m2.s

Prof. R. Shanthi

34

Example 6.5.2 from Ref. 1

Diffusion through a packging film using permeability:
A polythene film 0.00015 m (0.15 mm) thick is being considered
for use in packaging a pharmaceutical product at 30oC. If the
partial pressure of O2 outside the package is 0.21 atm and inside
it is 0.01 atm, calculate the diffusion flux of O2 at steady state.
Assume that the resistances to diffusion outside the film and
inside are negligible compared to the resistance of the film.
Permeability of O2 in polythene at 303 K is 4.17 x 10-12 m3 solute
(STP)/(s.m2.atm.m).
Answer: 2.480 x 10-12 kmol O2/m2.s
Would you prefer nylon to polythene? Permeability of O2 in nylon
at 303 K is 0.029 x 10-12 m3 solute (STP)/(s.m2.atm.m). Support
your answer.

Prof. R. Shanthi

35

Diffusion through a cylinder wall

Applying equation (33) for steady-state diffusion through a
cylinder wall of inner radius r1 and outer radius r2 and length L in
the radial direction outward, we get
Mass transfer per time
Mass transfer
per area per
nA
dCA
time
(35)
NA = 2 r L = -DAB
dr
Area of mass transfer
nA =

2L DAB(CA1 - CA2)
ln(r2 / r1)

Drive (36) and compare it with

heat conduction equivalent.
Prof. R. Shanthi

(36)

CA1
r2

CA2

r
r1

36

Diffusion through a spherical shell

Applying equation (33) for steady-state diffusion through a
spherical shell of inner radius r1 and outer radius r2 in the radial
direction outward, we get
Mass transfer per time
Mass transfer
per area per
nA
dCA
time
(37)
NA = 4 r2 = -DAB
dr
Area of mass transfer
nA = 4r1r2 DAB(CA1 - CA2)
(r2 - r1)
Drive (38) and compare it with
heat conduction equivalent.
Prof. R. Shanthi

(38)

CA1
r2

CA2

r
r1

37

Diffusion in porous solids

Read Section 6.5C (page 445 to 446) of Ref. 1

Prof. R. Shanthi

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