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Mass Transfer-principles and Applications

# Mass Transfer-principles and Applications

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04/20/2015

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Cadmium vapor is a toxic substance whose diffusivity in air is not readily
available in the literature. It is desired to calculate its diffusivity at its boiling
point of 1038 K and a pressure of 1 atm. Because an empirical atomic volume
is not available, we use the reported value for its liquid volume of 14 cm3

/

mol for an atomic weight of 112.4. We obtain, using Equation 3.2:

DAB = 1.6 cm2

/s

D

u

T
M

n
V

= µ

1
3 l

/

D

T

M

M

P

V

V

AB

A

B

T

A

B

= ¥

+

+

[

]

-

10010

1

1

3175

13

132

.

(/

/

)

(

)

(

)

.

/

/

S

S

D

AB =

+

Ê
ËÁ

ˆ
¯˜

+

[

]

-

101038

1
1124

1
29

1014

201

3

175

12

13

132

(

)

.

.

.

.

/

/

/

94

Mass Transfer: Principles and Applications

A data point for the diffusivity of Cd in N2 at 273 K is available for
comparison. Its value is 0.15 cm2

/s and we obtain, by applying a temperature

correction in line with Equation 3.2,

This is in good agreement with the calculated value of 1.6 cm2

/s.

Some remarks are in order regarding the magnitude of gas phase diffusivi-
ties. We note from Table 3.1 that at 25C and a pressure of 1 atm, most
diffusivities cluster around a value of 0.1 cm2

/s. This includes metal vapors,
as well as medium-sized organic molecules such as DDT and the PCBs. The
reason for this lies in the relatively weak dependence of DAB on molar volume
and mass and the limited number of gaseous or volatile substances available.
The larger organic molecules such as polymers, proteins, and carbohydrates
that would lead to low diffusivity values do not exist in the vapor phase.
Thus, gas diffusivities lower than 0.01 cm2

/s are unlikely to be encountered.
An upper ceiling is provided by the lightest molecules, hydrogen and
helium, which have a mutual diffusion coefﬁcient of 1.35 cm2

/s at 25C and
1 atm. A reasonable order-of-magnitude estimate can therefore be arrived at
in most cases by starting with a value of DAB = 0.1 cm2

/s and applying
temperature or pressure correction factors in accordance with Equation 3.2.

TABLE 3.2

Atomic and Molecular Volume Contributions for
Diffusivity Calculations

Species

Volume V (cm3

/mol)

A. Gases (Fuller, Schettler, and Giddings Method)

C

16.5

H

1.98

O

5.48

N

5.69

Cl

19.5

Aromatic ring

–20.2

Air

20.1

B. Liquids (Wilke–Chang Method)

C

14.8

H

3.7

O

7.4

O in high esters and others

11.0

O in acids (–OH)

12.0

Cl (terminal)

21.6

6-numbered ring

–15

D

AB = ¥ Ê

Ë ˆ

¯ =

0 15 1038

273 1 55

1 75

.

.

.

cm /s

2

Diffusion through Gases, Liquids, and Solids

95

Applying this procedure to the cadmium vapor of Illustration 3.1, we obtain
a value of

which is of the correct order of magnitude.

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