Mass Transfer Third Year Assist. Prof. Dr.

Ahmed Daham

Chapter (10) in Volume (1)

((Diffusion))
The term diffusion (mass transfer) is used to denote the transference of a component in
a mixture from a region where its concentration is high to a region where the concentration is
lower. Diffusion process can take place in a gas or vapour or in a liquid, and it can result from
the random velocities of the molecules (molecular diffusion) or from the circulating or eddy
currents present in a turbulent fluid (eddy diffusion).

Diffusion depends on:

1. Driving force (ΔC), moles per unit volume (kmol/m3).
2. The distance in the direction of transfer (Δz), meter (m).
3. Diffusivity coefficient, unit area per unit time (m2/s).

Fick's Law of diffusion:

The rate of diffusion is governed by Fick's Law, first proposed by Fick in 1855 which
expresses the mass transfer rate as a linear function of the molar concentration gradient. In a
mixture of two gases A and B, assumed ideal, Fick's Law for steady state diffusion may be
written as:
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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

∆CA
JA α
∆z

dCA
JA = − DAB ………… Fick ′ s first law of steady state diffusion
dz

Where:
kmol
JA : is the molecular diffusion flux of A , (moles per unit area per unit time) .
m 2 .s
kmol
CA: is the concentration of A (moles of A per unit volume) .
m3
DAB: is known as the diffusivity or diffusion coefficient for A in B (unit area per unit time)
m2
s
z: is distance in the direction of transfer (m).

Diffusion with bulk of mass in motion:

The Fick's first law of diffusion describes the mass transfer from the random movement
of molecules of a stationary medium or a fluid in streamline flow. If circulating currents or
eddies are present, then the molecular mechanism will be reinforced and the total mass
transfer rate may be written as:

Total diffusion = Molecular diffusion + Convection term

Convection term = Eddy diffusion = Molar flux due to convection

Convection term = Concentration * mass transfer velocity = CA . V

Where:
𝐤𝐦𝐨𝐥
𝐦𝐚𝐬𝐬 𝐟𝐥𝐮𝐱 𝐍𝐀 + 𝐍𝐁 𝟐 𝐦
𝐦𝐚𝐬𝐬 𝐭𝐫𝐚𝐧𝐬𝐟𝐞𝐫 𝐯𝐞𝐥𝐨𝐜𝐢𝐭𝐲 𝐕 = = = 𝐦 .𝐬 =
𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐂𝐓 𝐤𝐦𝐨𝐥 𝐬
𝐦 𝟑

Total diffusion = NA = JA + CA . V

𝐝𝐂𝐀 𝐂𝐀
𝐍𝐀 = −𝐃𝐀𝐁 + 𝐍𝐀 + 𝐍𝐁 … … … … … … … … … … … … … … … … (𝟏)
𝐝𝐳 𝐂𝐓

Total diffusion equation in the form of concentration (normally used for liquids)

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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

The total diffusion equation can be write in another forms:

a. Partial pressure for gases.

b. Mole fraction for gases and liquids.

a. Total diffusion equation in the partial pressure form:

If A and B are ideal gases in a mixture, the ideal gas law may be applied to each gas
separately and to the mixture:

n
PV=nRT P = RT
V

P =CRT
PA = CA R T and PT = CT R T

PA
CA =
RT
1
dCA = dP
RT A

−𝐃𝐀𝐁 𝐝𝐏𝐀 𝐏𝐀
𝐍𝐀 = + 𝐍𝐀 + 𝐍𝐁 … … … … … … … … … … … … … … … … (𝟐)
𝐑𝐓 𝐝𝐳 𝐏𝐓

Total diffusion equation in the form of partial pressure (normally used for gases)

b. Total diffusion equation in the mole fraction form:

PA CA
XA = or XA =
PT CT
PT XA = PA and CT XA = CA

PT dXA = dPA and CT dXA = dCA

Then:

− 𝐃𝐀𝐁 𝐏𝐓 𝐝𝐗 𝐀
𝐍𝐀 = + 𝐗 𝐀 𝐍𝐀 + 𝐍𝐁 … … … … … … … … … … … … … … … … (𝟑)
𝐑𝐓 𝐝𝐳

Total diffusion equation in the form of mole fraction (used for gases and liquids)

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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

Modes of diffusion
There are two modes of diffusion:

Diffusion

(1( (2(

Stagnant diffusion Counter diffusion

𝐍𝐁 = 𝟎

 In absorption
process (i( (ii(

Equimolecular Unequimolecular
Counter diffusion Counter diffusion

𝐍𝐁 = − 𝐍𝐀 𝐍𝐁 = −𝐧 𝐍𝐀

 In distillation  In chemical
column reaction

1. Stagnant diffusion (Mass transfer through a stationary second component):

In several important processes, one component in a gaseous mixture will be transported

relative to a fixed plane, such as a liquid interface, for example, and the other will undergo no
net movement. In gas absorption a soluble gas A is transferred to the liquid surface where it
dissolves, whereas the insoluble gas B undergoes no net movement with respect to the
interface. Similarly, in evaporation from a free surface, the vapour moves away from the
surface but the air has no net movement. The mass transfer process therefore:

−𝐃𝐀𝐁 𝐝𝐏𝐀 𝐏𝐀
𝐍𝐀 = + 𝐍𝐀 + 𝐍𝐁 … … … … … … … … … … … … … … … … (1)
𝐑𝐓 𝐝𝐳 𝐏𝐓

Since stagnant diffusion layer: NB = 0

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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

−𝐃𝐀𝐁 𝐝𝐏𝐀 𝐏𝐀
𝐍𝐀 = + 𝐍𝐀 … … … . … … … … … … … … … … … … … … … … (2)
𝐑𝐓 𝐝𝐳 𝐏𝐓

𝐏𝐀 −𝐃𝐀𝐁 𝐝𝐏𝐀
𝐍𝐀 𝟏 − = … … … … … … … . . . … … … … … … … … … … . … (3)
𝐏𝐓 𝐑𝐓 𝐝𝐳

−𝐃𝐀𝐁 𝟏 𝐝𝐏𝐀
𝐍𝐀 = … … … … … … … . . . … … … … … … … … … … . … (4)
𝐑𝐓 𝐝𝐳 𝐏
𝟏 − 𝐏𝐀
𝐓

−𝐃𝐀𝐁 𝐏𝐓 𝐝𝐏𝐀
𝐍𝐀 = … … … … … … … . . . … … … … … … … … … … . … (5)
𝐑𝐓 𝐝𝐳 𝐏𝐓 − 𝐏𝐀

𝐃𝐀𝐁 𝐏𝐓 𝐏𝐓 − 𝐏𝐀𝟐
𝐍𝐀 = 𝐥𝐧
𝐑𝐓 𝐳𝟐 − 𝐳𝟏 𝐏𝐓 − 𝐏𝐀𝟏

Example 10.1: Ammonia gas is diffusing at a constant rate through a layer of stagnant air
1 mm thick. Conditions are such that the gas contains 50 percent by volume ammonia at one
boundary of the stagnant layer. The ammonia diffusing to the other boundary is quickly
absorbed and the concentration is negligible at that plane. The temperature is 295 K and the
pressure atmospheric, and under these conditions the diffusivity of ammonia in air is 0.18
cm2/s. Estimate the rate of diffusion of ammonia through the layer.

Solution:
If the subscripts 1 and 2 refer to the two sides of the stagnant layer and the subscripts A and B refer
to ammonia and air respectively, then the rate of diffusion through a stagnant layer is given by:

𝐃𝐀𝐁 𝐏𝐓 𝐏𝐓 − 𝐏𝐀𝟐
𝐍𝐀 = 𝐥𝐧
𝐑𝐓 𝐳𝟐 − 𝐳𝟏 𝐏𝐓 − 𝐏𝐀𝟏

Where:

𝐏𝐓 = 101.3 kPa , 𝐏𝐀𝟐 = 0 , 𝐏𝐀𝟏 = yA PT = 0.5 ∗ 101.3 = 50.65 kPa

∆𝐳 = 𝐳𝟐 − 𝐳𝟏 = 1 mm = 1 ∗ 10−3 m

kJ 𝑐𝑚2 𝑚2
𝐑 = 8.314 , 𝐓 = 298 K and DAB = 0.18 = 1.8 ∗ 10−5
kmol . K 𝑠 𝑠

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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

1.8 ∗ 10−5 101.3 101.3 − 0 −4

kmol
𝐍𝐀 = ln = 5.153 ∗ 10
8.314 ∗ 295 1 ∗ 10−3 101.3 − 50.65 m2 . s

2. Counter diffusion:
i. Equimolecular counter diffusion:

When the mass transfer rates of the two components are equal and opposite the process
is said to be one of equimolecular counter diffusion. Such a process occurs in the case of the
box with a movable partition. It occurs also in a distillation column when the molar latent
heats of the two components are the same (λA = λB) . At any point in the column a falling
stream of liquid is brought into contact with a rising stream of vapour with which it is not in
equilibrium. The less volatile component is transferred from the vapour to the liquid and the
more volatile component is transferred in the opposite direction. If the molar latent heats of
the components are equal, the condensation of a given amount of less volatile component
releases exactly the amount of latent heat required to volatilize the same molar quantity of the
more volatile component. Thus at the interface, and consequently throughout the liquid and
vapour phases, equimolecular counter diffusion is taking place (NB = - NA).

−𝐃𝐀𝐁 𝐝𝐏𝐀 𝐏𝐀
𝐍𝐀 = + 𝐍𝐀 + 𝐍𝐁 … … … … … … … … … … … … … … … … (1)
𝐑𝐓 𝐝𝐳 𝐏𝐓

Since equimolecular counter diffusion: NB = - NA

−𝐃𝐀𝐁 𝐝𝐏𝐀 𝐏𝐀
𝐍𝐀 = + 𝐍𝐀 − 𝐍𝐀 … … … … … … … … … … … … … … … … (2)
𝐑𝐓 𝐝𝐳 𝐏𝐓

−𝐃𝐀𝐁 𝐝𝐏𝐀
𝐍𝐀 = … … … … … … … … … … … … … … … … (3)
𝐑𝐓 𝐝𝐳

−𝐃𝐀𝐁 𝐝𝐏𝐀
𝐍𝐀 = … … … … … … … … … … … … … … … … (4)
𝐑𝐓 𝐝𝐳

−𝐃𝐀𝐁 𝐏𝐀𝟐 − 𝐏𝐀𝟏

𝐍𝐀 = … … … … … … … … … … … … … … … … (5)
𝐑𝐓 𝐳𝟐 − 𝐳𝟏

𝐃𝐀𝐁 𝐏𝐀𝟏 − 𝐏𝐀𝟐

𝐍𝐀 =
𝐑𝐓 𝐳 𝟐 − 𝐳𝟏

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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

Drift Factor:
For stagnant diffusion:

DAB PT PT − PA 2
NA = ln
RT ∆z PT − PA 1

DAB PT PT − PA 2 − PT − PA 1 PT − PA 2
NA = ln
RT ∆z PT − PA 2 − PT − PA 1 PT − PA 1

From Dalton's Law of partial pressures: PT = PA + PB

By definition, PBm , the logarithmic mean of PB 1 and PB 2 , is given by:

PT − PA 2 − PT − PA 1 PB 2 − PB 1
= = PBm
PT − PA PB
ln P − P 2 ln P 2
T A1 B1

D AB 1 PT
NA = PA 1 − PA 2
RT ∆z P Bm

PT
Where: is known as the drift factor.
P Bm

PT
If the drift factor = = 1 ( this happen when the concentration of component A
P Bm
being transferred is low)

Then,

D AB PA −PA
1 2
NA =
RT z 2 −z 1

PT
* Thus the bulk flow enhances the mass transfer rate by a factor , known as
P Bm
the drift factor.

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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

Example: In an air-carbon dioxide mixture at 298 K and 202.6 kPa, the concentration of CO2
at two planes (3 mm) apart are 15 vol.% and 25 vol.%. The diffusivity of CO2 in air at 298 K
and 202.6 kPa is 8.2*10-6 m2/s. Calculate the rate of transfer of CO2 across the two planes,
assuming:

a. Equimolecular counter diffusion.

b. Diffusion of CO2 through a stagnant air layer.

Solution:
PA 1 = yA 1 . PT = 0.15 202.6 = 30.39 kPa
PA 2 = yA 2 . PT = 0.25 202.6 = 50.65 kPa

a. Equimolecular counter diffusion.

DAB PA1 − PA2
NA =
RT z2 − z1
8.2 ∗ 10−6 kmol
NA = 50.65 − 30.39 = 2.23 ∗ 10−5
8.314 298 (3 ∗ 10−6 ) m2 . s

b. Stagnant diffusion.

DAB PT PT − PA 2
NA = ln
RT ∆z PT − PA 1

8.2 ∗ 10−6 202.6 202.6 − 30.39 kmol

NA = ln = 2.79 ∗ 10−5
8.314 298 3 ∗ 10−6 202.6 − 50.65 m2 . s

ii. Unequimolecular counter diffusion:

When the mass transfer rates of the two components are unequal and opposite, the
process is said to be the unequimolecular diffusion, such a process occurs in a chemical
reaction.

−𝐃𝐀𝐁 𝐝𝐏𝐀 𝐏𝐀
𝐍𝐀 = + 𝐍𝐀 + 𝐍𝐁 … … … … … … … … … … … … … … … … (1)
𝐑𝐓 𝐝𝐳 𝐏𝐓

Since unequimolecular counter diffusion: NB = - n NA

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Mass Transfer Third Year Assist. Prof. Dr. Ahmed Daham

−𝐃𝐀𝐁 𝐝𝐏𝐀 𝐏𝐀
𝐍𝐀 = + 𝐍𝐀 − 𝐧 𝐍𝐀 … … … … … … … … … … … … … … … … (2)
𝐑𝐓 𝐝𝐳 𝐏𝐓

𝐏𝐀 −𝐃𝐀𝐁 𝐝𝐏𝐀
𝐍𝐀 𝟏 − 𝟏−𝐧 = … … … … … … … … … … … … … … … … (3)
𝐏𝐓 𝐑𝐓 𝐝𝐳

−𝐃𝐀𝐁 𝐏𝐓 𝐝𝐏𝐀
𝐍𝐀 = . . … … … … … … … … … . . … … … … … … (4)
𝐑𝐓 𝐝𝐳 𝐏
𝟏 − 𝐏𝐀 𝟏−𝐧
𝐓

−𝐃𝐀𝐁 𝟏 𝐝𝐏𝐀
𝐍𝐀 = . . … … … … … … … … … . . … … … … … … (5)
𝐑𝐓 ∆𝐳 𝐏𝐓 − 𝐏𝐀 𝟏 − 𝐧

𝐃𝐀𝐁 𝐏𝐓 𝟏 𝐏𝐓 − 𝟏 − 𝐧 𝐏𝐀𝟐
𝐍𝐀 = 𝐥𝐧
𝐑𝐓 ∆𝐳 𝟏−𝐧 𝐏𝐓 − 𝟏 − 𝐧 𝐏𝐀𝟏

Example: Species A in a gaseous mixture diffuses through a (3 mm) thick film and reaches a
catalyst surface where the reaction A → 3B takes place. If the partial pressure of A in the
bulk of the gas is 8.5 kN/m2 and the diffusivity of A is 2*10-5 m2/s. Find the mole flux of A,
given the pressure and temperature of the system are 101.3 kPa and 297 K, respectively.

Solution:
A → 3B
𝐍𝐁 𝟑
𝐧= = =𝟑
𝐍𝐀 𝟏

Given:
−5 m2
DAB = 2 ∗ 10 , PT = 101.3 kPa
s
T = 297 K , PA 1 = 8.5 kPa
PA 2 = 0

𝐃𝐀𝐁 𝐏𝐓 𝟏 𝐏𝐓 − 𝟏 − 𝐧 𝐏𝐀𝟐
𝐍𝐀 = 𝐥𝐧
𝐑𝐓 ∆𝐳 𝟏−𝐧 𝐏𝐓 − 𝟏 − 𝐧 𝐏𝐀𝟏
2 ∗ 10−5 101.3 1 101.3 + 2(0) kmol
𝐍𝐀 = ln = 2.12 ∗ 10−5
8.314 ∗ 297 3 ∗ 10−3 1−3 101.3 + 2(8.5) m2 . s

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