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Mass Transfer PDFelement

((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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∆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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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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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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−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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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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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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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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−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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Mass Transfer PDFelement

Maxwell's Law for multicomponent mass transfer

This argument can be applied to the diffusion of a constituent of a multicomponent gas.
Considering the transfer of component A through a stationary gas consisting of components
B, C, D, ... etc, if the total partial pressure gradient can be regarded as being made up of
a series of terms each representing the contribution of the individual component gases. The
mass transfer rate can be calculated from the previous equations using the effective diffusivity
of A in the mixture (DAm).

Calculation of the effective diffusivity of (A) in the mixture (DAm):

Let A be the diffusing species through stagnant mixture of B, C, D ….. etc.

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐦 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀 + 𝐍𝐁 + 𝐍𝐂 + 𝐍𝐃 … … … … … … … … … … (𝟏)
𝐝𝐳

Where: DAm is the effective diffusivity of A in the mixture.

Since stagnant diffusion layer of the mixture: NB = NC = ND = 0

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐦 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀 … … … … … … … … … … (𝟐)
𝐝𝐳

𝐍𝐀 𝟏 − 𝐗 𝐀 𝐝𝐗 𝐀
= − … … … … … … … … … … (𝟑)
𝐂𝐓 𝐃𝐀𝐦 𝐝𝐳

Now consider binary system for diffusion of A in B.

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐁 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀 + 𝐍𝐁
𝐝𝐳

Since stagnant diffusion layer: NB = 0

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐁 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀
𝐝𝐳

𝐝𝐗 𝐀
𝐍𝐀 𝟏 − 𝐗 𝐀 = − 𝐃𝐀𝐁 𝐂𝐓
𝐝𝐳

𝐍𝐀 𝟏 − 𝐗 𝐀 𝐝𝐗 𝐀
= −
𝐂𝐓 𝐃𝐀𝐁 𝐝𝐳

But: 𝟏 − 𝐗𝐀 = 𝐗𝐁 −𝐝𝐗 𝐀 = 𝐝𝐗 𝐁

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𝐍𝐀 𝐗 𝐁 𝐝𝐗 𝐁
= … … … … … … … … … … … … … … … … . . (𝟒)
𝐂𝐓 𝐃𝐀𝐁 𝐝𝐳

Similarly for diffusion of A in C.

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐂 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀 + 𝐍𝐂
𝐝𝐳

Since stagnant diffusion layer: NC = 0

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐂 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀
𝐝𝐳

𝐝𝐗 𝐀
𝐍𝐀 𝟏 − 𝐗 𝐀 = − 𝐃𝐀𝐂 𝐂𝐓
𝐝𝐳

𝐍𝐀 𝟏 − 𝐗 𝐀 𝐝𝐗 𝐀
= −
𝐂𝐓 𝐃𝐀𝐂 𝐝𝐳

But: 𝟏 − 𝐗𝐀 = 𝐗𝐂 −𝐝𝐗 𝐀 = 𝐝𝐗 𝐂

𝐍𝐀 𝐗 𝐂 𝐝𝐗 𝐂
= … … … … … … … … … … … … … … … … . . (𝟓)
𝐂𝐓 𝐃𝐀𝐂 𝐝𝐳

Similarly for diffusion of A in D.

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐃 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀 + 𝐍𝐃
𝐝𝐳

Since stagnant diffusion layer: ND = 0

𝐝𝐗 𝐀
𝐍𝐀 = − 𝐃𝐀𝐃 𝐂𝐓 + 𝐗 𝐀 𝐍𝐀
𝐝𝐳

𝐝𝐗 𝐀
𝐍𝐀 𝟏 − 𝐗 𝐀 = − 𝐃𝐀𝐃 𝐂𝐓
𝐝𝐳

𝐍𝐀 𝟏 − 𝐗 𝐀 𝐝𝐗 𝐀
= −
𝐂𝐓 𝐃𝐀𝐃 𝐝𝐳

But: 𝟏 − 𝐗𝐀 = 𝐗𝐃 −𝐝𝐗 𝐀 = 𝐝𝐗 𝐃

𝐍𝐀 𝐗 𝐃 𝐝𝐗 𝐃
= … … … … … … … … … … … … … … … … . . (𝟔)
𝐂𝐓 𝐃𝐀𝐃 𝐝𝐳

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Now adding Equations (4), (5) and (6):

𝐍𝐀 𝐗𝐁 𝐗𝐂 𝐗𝐃 𝐝(𝐗 𝐁 + 𝐗 𝐂 + 𝐗 𝐃 )
+ + =
𝐂𝐓 𝐃𝐀𝐁 𝐃𝐀𝐂 𝐃𝐀𝐃 𝐝𝐳

But: 𝐗𝐁 + 𝐗𝐂 + 𝐗𝐃 = 𝟏 − 𝐗𝐀

𝐝(𝐗 𝐁 + 𝐗 𝐂 + 𝐗 𝐃 ) 𝐝𝐗 𝐀
=−
𝐝𝐳 𝐝𝐳
𝐍𝐀 𝐗 𝐁 𝐗𝐂 𝐗𝐃 𝐍𝐀 𝟏 − 𝐗 𝐀
+ + =
𝐂𝐓 𝐃𝐀𝐁 𝐃𝐀𝐂 𝐃𝐀𝐃 𝐂𝐓 𝐃𝐀𝐦

𝟏 − 𝐗𝐀 𝐗𝐁 𝐗𝐂 𝐗𝐃
= + +
𝐃𝐀𝐦 𝐃𝐀𝐁 𝐃𝐀𝐂 𝐃𝐀𝐃

For dilute mixture (low concentration of A), XA → 0

𝟏 𝐗𝐁 𝐗𝐂 𝐗𝐃
= + +
𝐃𝐀𝐦 𝐃𝐀𝐁 𝐃𝐀𝐂 𝐃𝐀𝐃

Example: Nitrogen is diffusing under steady condition through a mixture of 2% N2, 20%
C2H6 , 30% C2H4 and 48% C4H10 at 298 K and 100 kPa. The partial pressure of nitrogen at
two planes (1 mm ) apart are 13.3 & 6.67 kPa, respectively. Calculate the rate of N2 across the
two planes. The diffusivity of N2 through C4H10 , C2H6 and C2H4 may be taken as 9.6*10-6
m2/s , 14.8*10-6 m2/s and 16.3*10-6 m2/s, respectively.

Solution:
Since stagnant diffusion:
DAm PT PT − PA 2
NA = ln
RT ∆z PT − PA 1

1 − yA yB yC yD
= + +
DAm DAB DAC DAD

1 − 0.02 0.48 0.2 0.3

= −6
+ −6
+
DAm 9.6 ∗ 10 14.8 ∗ 10 16.3 ∗ 10−6

−5
m2
DAm = 1.22 ∗ 10
s
1.22 ∗ 10−5 100 100 − 6.67 kmol
NA = ln = 0.0492
8.314 ∗ 298 0.001 100 − 13.3 m2 . s
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Diffusivities of gases and vapours

Experimental values of diffusivities are given in Table 10.2 for a number of gases and
vapours in air at 298K and atmospheric pressure. The table also includes values of the
Schmidt number Sc, the ratio of the kinematic viscosity (μ/A) to the diffusivity (D) for very
low concentrations of the diffusing gas or vapour. The importance of the Schmidt number in
problems involving mass transfer is discussed later.

Experimental determination of diffusivities

Diffusivities of vapours are most conveniently determined by the method developed by

Winkelmann in which liquid is allowed to evaporate in a vertical glass tube over the top of
which a stream of vapour-free gas is passed, at a rate such that the vapour pressure is
maintained almost at zero (Figure 10.2). If the apparatus is maintained at a steady
temperature, there will be no eddy currents in the vertical tube and mass transfer will take
place from the surface by molecular diffusion alone. The rate of evaporation can be followed
by the rate of fall of the liquid surface, and since the concentration gradient is known, the
diffusivity can then be calculated.

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

D AB 1 PT
NA = PA 1 − PA 2
RT z P Bm

D AB CT
NA = CA 1 − CA 2
z C Bm

Material balance on component A over dz:

In = out ( in kg)
(A * dz) ρL =NA * A * M.wt * dt out

ρL dz dz
NA = … … … … … … … . . (2)
Mwt dt

in
Substitute Eq.(1) in to Eq.(2). To get:

ρL dz DAB PT PT − PA 2
= ln
Mwt dt RT z PT − PA 1

t z2
DAB PT PT − PA 2 ρL
ln dt = z dz
RT ∆z PT − PA 1 Mwt
0 z1

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ρL . z2 2 − z1 2 . RT
DAB =
PT − PA 2
Mwt . 2t . PT . ln
PT − PA 1

Where:
ρL is the liquid density (kg/m3).
Mwt is the molecular weight of liquid.
PA 2 = 0 (always).

DAB CT
NA = CA 1 − CA 2 … … … … … … … … … … … … . (3)
z CBm

Since PA 2 = CA 2 = 0
Let CA 1 = CA

CA CT
NA = DAB … … … … … … … … … … … … … (4)
z CBm

Substitute Eq.(4) in to Eq.(2). To get:

ρL dz C CT
= DAB A
Mwt dt z CBm

2 Mwt . DAB . CA CT
z2 2 − z1 2 = t
ρL CBm
2 Mwt . DAB . CA CT
z2 − z1 (z2 − z1 + 2z1 ) = t
ρL CBm

𝐭 𝛒𝐋 𝐂𝐁𝐦
= 𝐳𝟐 − 𝐳𝟏
𝐳𝟐 − 𝐳𝟏 𝟐 𝐌𝐰𝐭 . 𝐃𝐀𝐁 . 𝐂𝐀 𝐂𝐓
𝛒𝐋 𝐂𝐁𝐦
+ 𝐳𝟏
𝐌𝐰𝐭 . 𝐃𝐀𝐁 . 𝐂𝐀 𝐂𝐓

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𝐭
If we draw against 𝐳𝟐 − 𝐳𝟏 then:
𝐳𝟐 −𝐳𝟏

ρL CBm
The slope s =
2 Mwt . DAB . CA CT

𝛒𝐋 𝐂𝐁𝐦
𝐃𝐀𝐁 =
𝟐 𝐌𝐰𝐭 . 𝐬𝐥𝐨𝐩𝐞 . 𝐂𝐀 𝐂𝐓

Example 10.2: The diffusivity of the vapour of a volatile liquid in air can be conveniently
determined by Winkelmann's method in which liquid is contained in a narrow diameter
vertical tube, maintained at a constant temperature, and an air stream is passed over the top of
the tube sufficiently rapidly to ensure that the partial pressure of the vapour there remains
approximately zero. On the assumption that the vapour is transferred from the surface of the
liquid to the air stream by molecular diffusion alone, calculate the diffusivity of carbon
tetrachloride vapour in air at 321 K and atmospheric pressure from the experimental data
given in Table 10.3.

The vapour pressure of carbon tetrachloride at 321 K is 37.6 kN/m2 and the density of the
liquid is 1540 kg/m3. The kilogram molecular volume may be taken as 22.4 m3.

Solution:
𝐭 𝛒𝐋 𝐂𝐁𝐦
= 𝐳𝟐 − 𝐳𝟏
𝐳𝟐 − 𝐳𝟏 𝟐 𝐌𝐰𝐭 . 𝐃𝐀𝐁 . 𝐂𝐀 𝐂𝐓
𝛒𝐋 𝐂𝐁𝐦
+ 𝐳𝟏
𝐌𝐰𝐭 . 𝐃𝐀𝐁 . 𝐂𝐀 𝐂𝐓

𝐭
we draw against 𝐳𝟐 − 𝐳𝟏
𝐳𝟐 −𝐳𝟏

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𝛒𝐋 𝐂𝐁𝐦
𝐃𝐀𝐁 =
𝟐 𝐌𝐰𝐭 . 𝐬𝐥𝐨𝐩𝐞 . 𝐂𝐀 𝐂𝐓

ks s
𝐓𝐡𝐞 𝐬𝐥𝐨𝐩𝐞 𝐬 = 0.031 2
= 3.1 ∗ 107 2
mm m

1 273 kmol
𝐂𝐓 = = 0.038
22.4 321 m3
PT 101.3 kmol
or, CT = = = 0.038
RT 8.314∗321 m3

Mwt = 154 kg/kmol , 𝛒𝐋 = 1540 kg/m3

𝐂𝐀 = mole fraction ∗ 𝐂𝐓

PA 37.6 kmol
𝐂𝐀 = CT = 0.038 = 0.0141
PT 101.3 m3

𝐂𝐁𝟏 = 𝐂𝐓 − 𝐂𝐀𝟏 = 0.038 − 0.0141 = 0.0239

𝐂𝐁𝟐 = 𝐂𝐓 − 𝟎 = 0.038

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𝐂𝐁𝟐 − 𝐂𝐁𝟏 0.038 − 0.0239 kmol

𝐂𝐁𝐦 = = = 0.0303
𝐂𝐁𝟐 0.038 m3
ln ln
𝐂𝐁𝟏 0.0239

1540 0.0303 −6
m2
𝐃𝐀𝐁 = = 9.12 ∗ 10
2 154 3.1 ∗ 107 (0.0141) 0.038 s

Example: A small diameter tube closed at one end was filled with acetone to within 18 mm
of the top and maintained at 290 K with a gentle stream of air blowing across the top. After
15000 sec, the liquid level was fallen to 27.5 mm, the vapour pressure of acetone was 21.95
kPa and atmospheric pressure was 99.75 kPa. Calculate the diffusivity of acetone in air.
Given: the density of acetone is 790 kg/m3 and the molecular weight of acetone is 58
kg/kmol.

Solution:

ρL . z2 2 − z1 2 . RT
DAB =
PT − PA 2
Mwt . 2t . PT . ln
PT − PA 1

790 0.02752 − 0.0182 8.314 (290) −5

m2
DAB = = 1.9 ∗ 10
99.75 − 0 s
58 . 15000 (99.75) . ln
99.75 − 21.95

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