Chapter 11

Mass Transfer by Diffusion

Theory

As with heat transfer, the rate of the transferred quantity in mass transfer is
proportional to the driving force and inversely proportional to the resistance.
For mass transfer by diffusion, the driving force is the chemical potential
difference; but concentration (mol/m3), mole fraction, or pressure differences
are usually used. Thus, the mass transfer rate is:

driving force
ci

ni
resistance R

For gases:

Driving
force Resistance, R

z
Equimolar Counterdiffusion
pi RG T
Di j A

Diffusion of i through stagnant j
pi
z pj M

RG T
Di j A P

For liquids:

Driving force Resistance, R

Equimolar Counterdiffusion
xi
z 1

Di j A cm

Diffusion of i through stagnant j
xi
z xj M

Di j A c m

S. Yanniotis, Solving Problems in Food Engineering. 141

Springer 2008
142 11 Mass Transfer by Diffusion

For solids:

Mass transfer rate

ci
For a single wall ni
R

ci
For a composite wall ni P
R

Resistance, R Surface area, A

z
Flat wall A
DA
Cylindrical wall
r A1 A2
ALM
DALM ln A1 =A2

r p
Spherical wall AG A1 A2
DAG

Flat packaging films:

Resistance, R Surface area, A

z
For gases 22414 A
PM A

z
For water vapor PM WV  A A

where

A = surface area perpendicular to the direction of transfer, m2

ALM = logarithmic mean of surface area A1 and A2, m2
AG = geometric mean of surface area A1 and A2, m2
ci = concentration of i, mol/m3
cm = mean concentration of i and j, mol/m3
D = diffusion coefficient, m2/s
Dij = diffusion coefficient of i in j, m2/s
ni= mass transfer flux, rate, mol/s
P = total pressure, Pa
pi = partial pressure of i, Pa
pjM = logarithmic mean pressure difference of j, Pa
PM = gas permeability, cm3 cm/s cm2 atm
PM WV = water vapor permeability, g cm/s cm2 Pa
RG = ideal gas constant, m3 Pa/mol K
T = temperature, K
Review Questions 143

xi = mol fraction of i
xjM = logarithmic mean mol fraction of j

z and
r = wall thickness, m

Review Questions

Which of the following statements are true and which are false?
1. Ficks 1st law refers to mass transfer by diffusion at steady state.
2. Molecular diffusion is a phenomenon analogous to heat transfer by
conduction.
3. The resistance to mass transfer increases linearly with diffusivity.
4. Mass diffusivity has the same units as thermal diffusivity and kinematic
viscosity.
5. Diffusivity in gasses is about 10000 times higher than in liquids.
6. Diffusivity does not vary with temperature.
7. Diffusivity in solids may vary with concentration.
8. The driving force for mass transfer by molecular diffusion is the difference
in chemical potential.
9. There is bulk flow in equimolar counterdiffusion.
10. In equimolar counterdiffusion Ni=Nj, where Ni and Nj are the fluxes of
gas i and gas j with respect to a fixed position.
11. There is no bulk flow in the case of diffusion of gas i through stagnant
nondiffusing gas j.
12. For the same driving force, the flux Ni in equimolar counterdiffusion is
smaller than Ni in diffusion of i through stagnant nondiffusing j due to the
bulk motion of i.
13. When concentrations are dilute, the bulk flow may be negligible.
14. Permeability refers to the diffusion of a gas in a solid and is used extensively
in calculating mass transfer in packaging materials.
15. Permeability is equal to the product of the diffusion coefficient and the
solubility of the gas in the solid.
16. The difference in partial pressure inside and outside the
packaging material is being used as the driving force for mass transfer
calculations.
17. Permeability decreases as the temperature increases.
18. Layers of different materials may be combined in laminates to give a
composite material with good barrier properties for water vapor, gasses,
and light.
19. Polyethylene is a good water vapor barrier and serves as an adhesive to the
next layer.
20. Aluminum foil is a good gas barrier
144 11 Mass Transfer by Diffusion

Examples
Example 11.1

Water vapor is diffusing through a stagnant film of air at 308C towards a

cold surface at 68C, where it is condensed. Calculate the water vapor
diffusion flux if the pressure is 1 atm, the water vapor pressure 10 mm from
the cold surface is 3 kPa, and the water vapor diffusion coefficient in the air is
0.26 cm2/s.
Solution
Step 1
Draw the process diagram:

pA1 = 3 kPa
pB1
Z =10 mm

P =1 atm
pA2
pB2
6C

air molecule water molecule

Step 2
State your assumptions:
l The system is at steady state.
l There are no eddies.
Step 3
Select the appropriate equation to calculate the water vapor diffusion flux.
Water molecules diffuse towards the cold plate; air molecules diffuse in the
opposite direction. There is a bulk movement towards the cold plate to keep the
system at constant pressure. Therefore the equation to use is:

nw pw1 pw2 pw1 pw2 Daw P

Nw p p
A RA
z a M
p RG T
z pa M w1 w2
Daw A P RG T A

(with subscript w for water vapor and a for air).

Examples 145

Step 4
Find the values of partial pressure to use in the above equation:

i) The water vapor partial pressure at the interphase at 68C is

pw2 0:935 kPafrom steam tables:

ii) The partial pressure of air is

pa1 101325  3000 98325 Pa

and

pa2 101325  935 100390 Pa

pa1 pa2 98325  100390

pa M p 99353:9 Pa
ln a1 98325
pa2 ln
100390

Comment: The arithmetic mean instead of the log mean could have been used
with very little error, since pa1 and pa2 values differ from one another by a small
percentage.

Step 5
Substitute values and calculate the water vapor diffusion flux:

Daw P
Nw p  pw2
R T z paM w1
 
0:26x104 m2 =s 101325 Pa
3000  935Pa
8314:34 m3 Pa=kmol K 303 K 0:01 m 99353:9 Pa
2:17x106 kmol=s m2

Example 11.2

A food product is sealed in a flexible laminated package with 0.1 m2

surface area that is made of a polyethylene film layer 0.1 mm thick and a
polyamide film layer 0.1 mm thick. The package is stored at 218C and 75%
relative humidity. Calculate the transfer rate of oxygen and water
146 11 Mass Transfer by Diffusion

vapor through the film at steady state if the partial pressure of O2 inside the
package is 0.01 atm, that outside the package is 0.21 atm, and the
water activity of the product inside the package is 0.3. The permeability
(PM) of polyethylene and polyamide to O2 are 22801011 and 51011 cm3/
(s cm2 atm /cm) respectively, and the water vapor transmission rate (WVTR)
for these materials measured at 37.88C using 90% RH water vapor source
and 0% RH desiccant sink are 61011 and 371011 g/(s cm2 /cm)
respectively.

Solution
Step 1
State your assumptions:

l The convective resistance to mass transfer on the two sides of the

package are negligible compared to the diffusion resistance of the
film.
l The WVTR at 218C does not differ appreciably from that at 37.88C.

Step 2
Calculate the diffusion rate of oxygen:

i) Select the equation to use:

p
nO2 P O2
R

ii) Substitute values and calculate the diffusion rate:

X
R R polyethylene R polyamid
 
22414
z polyeth: 22414
z polyam: 22414
z polyeth:
z polyam:

A PM polyeth: A PM polyam: A PM polyeth: PM polyam:
 
22414 cm3 =mol 0:01 cm
 11

1000 cm2 2280  10 cm3 cm=s cm2 atm
!
0:01 cm
 
5  1011 cm3 cm=s cm2 atm

9:83  106 4:48  109 4:49  109 atm s=mol

p 0:21  0:01 atm

n O2 P O2 4:45  1011 mol=s
R 4:49  109 atm s=mol
Examples 147

Step 3
Calculate the diffusion rate of water vapor.

i) Select the equation to use:

p
nw P w
R

with pw the water vapor difference between the inside and the outside of
the package and

z
R
PM WV A

ii) Find the water vapor pressure inside and outside the package.
The water vapor pressure pw at 218C is 2487 Pa (from steam tables).
The water vapor partial pressure outside the package for 75% relative
humidity is:

75
pw o 2487 1865:3 Pa
100

The water vapor partial pressure inside the package for water activity 0.3 is:

pw i 0:3 x 2487 746:1 Pa

iii) Calculate the water vapor permeability.

Water vapor permeability for polyethylene can be calculated from the
Water Vapor Transmission Rate as:

WVTRpolyeth: 6  1011 g cm=s cm2

PM WV polyethylene

p 0:90  6586  0 Pa
1:01  1014 g cm=s cm2 Pa

Similarly for polyamide:

WVTRpolyeth: 37  1011 g cm=s cm2

PM WV polyamid

P 0:90  6586  0 Pa
6:24  1014 g cm=s cm2 Pa
148 11 Mass Transfer by Diffusion

iv) Calculate the total resistance to water vapor transfer for the laminate:

X
zpolyeth:
zpolyamid
R Rpolyet h y l e ne Rpolyamid
PM WV polyeth: A PM WV polyamid A
0:01 cm
 
1:01  1014 g cm=s cm2 Pa 1000 cm2
0:01 cm
 
6:24  1014 g cm=s cm2 Pa 1000 cm2
9:90  108 1:60  108 1:15  109 Pa s=g

v) Calculate the water vapor transfer rate:

p 1865:3  746:1 Pa
nw P w 9:73  107 g=s
R 1:15  109 Pa s =g

Comment: Notice that the polyethylene film layer contributes the main resis-
tance to water vapor transfer (86.1%), while polyamide contributes the main
resistance to oxygen transfer (99.8%).

Exercises

Exercise 11.1

Water evaporates from the flat surface of the leaf of a vegetable and is
diffusing away through a stagnant layer of air. The total pressure is 101325
Pa and the temperature is 248C. Calculate the evaporation rate in g/s under
the following conditions: water activity (aw) of the leaf surface is 0.98, partial
water vapor pressure 5 mm away from the surface of the leaf is 2100 Pa,
surface area of the leaf is 50 cm2. The diffusion coefficient of water vapor in
air is 2.6105 m2/s.

Solution
Step 1
State your assumptions:
The time interval the calculations are based on is small so that the water
vapor pressure at the surface of the leaf is constant and the system is at
steady state.
Exercises 149

Step 2
Select the equation to use:
Since water vapor diffuses through a stagnant layer of air, the equation to be
used is:

Nw :::::::::::::::::::::::::::::::::::::::::::::::::::

Step 3
Find the water vapor pressure pw at 248C from the steam tables: ....................
Calculate the partial water vapor pressure pw1 at the surface of the leaf as:

pw1 aw : pw :::::::::::::::::::::::::::::::::::::

Step 4
Calculate the partial pressure of air:

pa1 P  pw1 :::::::::::::::::::::::::::::::::::::::::::::::

pa2 ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

paM :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

Step 5
Calculate the mass transfer flux:

Nw ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::kmol=s m2

Step 6
Calculate the evaporation rate:

nw ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::g=s

Exercise 11.2

An aroma compound is encapsulated in a nonporous spherical particle made of

a homogenous biopolymer film. Calculate the aroma release rate if the particle
diameter is 1 mm, the film thickness is 0.1 mm, the concentration of the aroma
compound is 0.1 g/cm3 and 0.01g/cm3 on the inside and outside surface of the
particle respectively, and the diffusion coefficient of the aroma compound in the
film is 11012 m2/s.
150 11 Mass Transfer by Diffusion

Solution
Step 1
Draw the process diagram:

r1
C2 C1 r2

A1 A2

Step 2
State your assumptions:

l The aroma release rate is diffusion-controlled.

l The release rate is constant (steady state).

Step 3
Calculate the resistance to mass transfer in a spherical wall.
i) Calculate the geometric mean area of A1 and A2:

A1 pD2 :::::::::::::::::::::::::::::::::::::::::::::::::

A2 ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

AG :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

ii) Calculate the resistance:

r
R :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
DAG

Step 4
Calculate the diffusion rate through the wall of the sphere:

n :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Exercises 151

Exercise 11.3

The solubility and the diffusivity of O2 in polyvinyl chloride are 3.84x104 cm3
O2 at STP/cmHg.cm3 solid and 1.18x1012 m2/s respectively. Calculate the
permeability of polyvinyl chloride to O2.
Solution
The permeability is the product of solubility and diffusivity. Therefore:

cm3 cm
PM S:D ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
s cm2 Pa

Exercise 11.4

A supplier of frozen hamburger patties is thinking of packaging them in 0.1 mm

thick polypropylene film. The permeability of polypropylene to O2 and water
vapor is 1x108 cm3/(s cm2 atm /cm) and 8x1015 g/(s cm2 Pa/cm) respectively.
The partial pressure of O2 is 0 atm and that of water vapor is 0.12 Pa inside the
package, while outside the package the partial pressure of O2 is 0.21 atm and
that of water vapor is 0.04 Pa. Calculate how much oxygen and how much
water vapor will pass through the polypropylene film of 600 cm2 surface area in
one week.

Solution
Step 1
Sate your assumptions:
l The convective resistance to mass transfer on the two sides of the
package is negligible compared to the diffusion resistance of the film.
l ..............................................................................................................

Step 2
Calculate the transfer rate of O2.
i) Calculate the resistance:

R ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

ii) Calculate the transfer rate of oxygen:

nO2 :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::mol=s

Step 3
Calculate the total amount of O2 that will diffuse into the package in one week:

mO2 ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: g
152 11 Mass Transfer by Diffusion

Step 4
Calculate the transfer rate of water vapor.
i) Calculate the resistance:
R :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

ii) Calculate the transfer rate of water vapor:

nw ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::g=s

Step 5
Calculate the total amount of water vapor that will diffuse out of the package in
one week:
mw ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: g

Exercise 11.5

Meat is packaged in a plastic disk covered with PVC film. Calculate the required
thickness of the film so that 1104 mol of oxygen enters the package through
the film in 24 hours. The permeability of PVC to oxygen is 4561011 cm3/
(s cm2 atm /cm), the surface area of the film is 300 cm2, and the partial pressure
of oxygen inside and outside the package is 0 atm and 0.21 atm respectively.

Solution
Step 1
State your assumptions:
..........................................................................................................................

Step 2
Calculate the mass transfer rate in mol/s:

nO2 :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

Step 3
Calculate the required resistance:

R ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

Step 4
Calculate the required thickness of the film

PM A

z R :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
22414
Exercises 153

Exercise 11.6

Potato chips are packed in a plastic bag in a nitrogen atmosphere. Calculate the
amount of N2 that will diffuse out of the plastic bag in 3 months if the thickness
of the film is 0.05 mm, the absolute pressure of N2 in the bag is 1.05 atm, the
surface area of the bag is 1000 cm2, and the permeability of the plastic film to N2
is 1.51010 cm3/s cm2 atm/cm.
Solution
Step 1
State your assumptions:
..........................................................................................................................
Step 2
Calculate the resistance:

R :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::

Step 3
Calculate the transfer rate of N2:

nN2 :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::mol=s

Step 4
Calculate the total amount of N2 that will diffuse out of the package in three
months:

mN2 :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: g

Verify that the pressure in the bag will not change appreciably due to N2
diffusion.
Hint: Use the ideal gas law.