11/03/2024

Chapter 2

DIFFUSION

Dr. Enshirah Da'na 1

INTRODUCTION
• Separation of components in a mixture is achieved by contacting
it with another insoluble phase.
• When transfer of the component from one phase to the other
occurs due to concentration gradient, the phenomenon is called
diffusion.
• The diffusion stops once equilibrium is attained.

Types of diffusion:
1. Molecular diffusion
2. Eddy diffusion or Turbulent diffusion

Dr. Enshirah Da'na 2

1
 11/03/2024

MOLECULAR DIFFUSION AND EDDY DIFFUSION

• Molecular diffusion can be defined as the movement of individual
molecules in a highly zigzag manner through another fluid.

• Molecular diffusion is Random process since the molecular

movement is in a random path.

• If a coloured solution is introduced in a pool of water, it begins

slowly to diffuse into the entire liquid which is termed as molecular
diffusion.

• To enhance its rate of mixing, a mechanical agitation is provided

and this will cause a turbulent motion.

Dr. Enshirah Da'na 3

• This method of mass transfer is known as eddy or turbulent or

convective diffusion.

Dr. Enshirah Da'na 4

2
 11/03/2024

DIFFUSIVITY OR DIFFUSION COEFFICIENT

• The driving force for diffusion to occur is concentration gradient.
• Fick’s first law of diffusion, which states that molar flux is directly
proportional to the concentration gradient.

Dr. Enshirah Da'na 5

𝝏𝑪𝑨 𝝏𝒙𝑨
𝑱𝑨 = −𝑫𝑨𝑩 = −𝒄𝑫𝑨𝑩
𝝏𝒛 𝝏𝒛
𝑱𝑨 is molar flux in moles/(area)(time).
𝑫𝑨𝑩 is diffusion coefficient or diffusivity in area/time.
𝝏𝑪𝑨
𝝏𝒛
is concentration gradient.
C is molar concentration of A and B in moles/vol.
𝒙𝑨 is mole fraction of A in the mixture.

• The –ve sign indicates the drop in concentration with respect to

distance (the movement from high concentration to low concentration).

Dr. Enshirah Da'na 6

3
 11/03/2024

Example 1
A mixture of He and N2 gas is contained in a pipe at 298 K and 1 atm
total pressure which is constant throughout. At one end of the pipe at
point 1 the partial pressure pA1 of He is 0.6 atm and at the other end 0.2
m pA2 = 0.2 atm. Calculate the flux of He at steady state if DAB of the He-
𝒎𝟐 𝒄𝒎𝟐
N2 mixture is 𝟎. 𝟔𝟖𝟕×𝟏𝟎'𝟒 𝒔
𝟎. 𝟔𝟖𝟕 𝒔
.

𝑷𝑽 = 𝒏𝑹𝑻
𝒏 𝑷
=𝒄=
𝑽 𝑹𝑻
Where n is the mol of (A + B), V is volume in m3, T is temperature in K,
R is 8314.3 m3.Pa/mol.K or R is 82.057×𝟏𝟎'𝟑 m3.atm/mol.K, and c is
mol (A + B)/m3. 7

Solution 𝝏𝒙𝑨
𝑱𝑨𝒛 = −𝒄𝑫𝑨𝑩
𝝏𝒛
𝒛𝟐 𝒄𝑨𝟐
𝑱𝑨𝒛 6 𝝏𝒛 = −𝑫𝑨𝑩 6 𝝏𝒄𝑨
𝒛𝟏 𝒄𝑨𝟏

𝒄𝑨𝟐 − 𝒄𝑨𝟏
𝑱𝑨𝒛 = −𝑫𝑨𝑩
𝒛𝟐 − 𝒛𝟏
𝒄𝑨𝟏 − 𝒄𝑨𝟐
𝑱𝑨𝒛 = 𝑫𝑨𝑩
𝒛𝟐 − 𝒛𝟏
𝒑𝑨𝟏 𝒏𝑨
𝒄𝑨𝟏 = =
𝑹𝑻 𝑽
𝑷𝑨𝟏 − 𝑷𝑨𝟐
𝑱𝑨𝒛 = 𝑫𝑨𝑩
𝑹𝑻 𝒛𝟐 − 𝒛𝟏 8

4
 11/03/2024

𝒑𝑨𝟏 = 𝟎. 𝟔 𝒂𝒕𝒎 = 𝟎. 𝟔×𝟏. 𝟎𝟏𝟑𝟐𝟓×𝟏𝟎𝟓 = 𝟔. 𝟎𝟖×𝟏𝟎𝟒 𝑷𝒂

𝒑𝑨𝟐 = 𝟎. 𝟐 𝒂𝒕𝒎 = 𝟎. 𝟐×𝟏. 𝟎𝟏𝟑𝟐𝟓×𝟏𝟎𝟓 = 𝟐. 𝟎𝟐𝟕×𝟏𝟎𝟒 𝑷𝒂

'𝟒
𝟔. 𝟎𝟖×𝟏𝟎𝟒 − 𝟐. 𝟎𝟐𝟕×𝟏𝟎𝟒
𝑱𝑨𝒛 = 𝟎. 𝟔𝟖𝟕×𝟏𝟎
𝟖𝟑𝟏𝟒 𝟐𝟗𝟖 𝟎. 𝟐 − 𝟎

𝒎𝒐𝒍𝑨
𝑱𝑨𝒛 = 𝟓. 𝟔𝟑×𝟏𝟎'𝟔
𝒔. 𝒎𝟐

Molecular diffusion in gases

Equimolar counter diffusion in gases
Two gases A and B at constant total pressure P in two large chambers
connected by a tube where molecular diffusion at steady state is
occuring.
Stirring in each chamber keeps the concentrations in each chamber
uniform.
𝑱𝑨 = −𝑱𝑩

𝑷 = 𝒑𝑨 + 𝒑𝑩 = 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑪 = 𝑪𝑨 + 𝑪𝑩
Differentiating both sides,
𝝏𝑪𝑨 = −𝝏𝑪𝑩
Dr. Enshirah Da'na 10

10

5
 11/03/2024

𝒑𝑨𝟏 > 𝒑𝑨𝟐

𝒑𝑩𝟐 > 𝒑𝑩𝟏

𝝏𝒄𝑩
𝑱𝑩 = −𝑫𝑩𝑨
𝝏𝒛
𝝏𝑪𝑨 𝝏𝑪𝑩
𝑱𝑨 = −𝑫𝑨𝑩 = −𝑱𝑩 = 𝑫𝑩𝑨
𝝏𝒛 𝝏𝒛

𝑫𝑨𝑩 = 𝑫𝑩𝑨

Dr. Enshirah Da'na 11

11

Example 2
Ammonia gas (A) is diffusing through a uniform tube 0.10 m long
containing N2 gas (B) at 𝟏. 𝟎𝟏𝟑𝟐×𝟏𝟎𝟓 Pa and 298 K. At point 1, 𝒑𝑨𝟏
= 𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟒 Pa and at point 2, 𝒑𝑨𝟐 = 𝟎. 𝟓𝟎𝟕×𝟏𝟎𝟒 Pa. The diffusivity
𝒎𝟐
𝑫𝑨𝑩 = 𝟎. 𝟐𝟑𝟎×𝟏𝟎'𝟒 𝒔 .
a) Calculate the flux 𝑱𝑨 at steady state.
b) Repeat for 𝑱𝑩 .

Dr. Enshirah Da'na 12

12

6
 11/03/2024

𝑷𝑨𝟏 − 𝑷𝑨𝟐
Solution 𝑱𝑨 = 𝑫𝑨𝑩
𝑹𝑻 𝒛𝟐 − 𝒛𝟏

'𝟒
𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟒 − 𝟎. 𝟓𝟎𝟕×𝟏𝟎𝟒
𝑱𝑨 = 𝟎. 𝟐𝟑𝟎×𝟏𝟎
𝟖𝟑𝟏𝟒 𝟐𝟗𝟖 𝟎. 𝟏 − 𝟎

𝒎𝒐𝒍 𝑨
𝑱𝑨 = 𝟒. 𝟕𝟎×𝟏𝟎'𝟕
𝒔. 𝒎𝟐

𝒑𝑩𝟏 = 𝑷 − 𝒑𝑨𝟏

𝒑𝑩𝟏 = 𝟏. 𝟎𝟏𝟑𝟐𝟓×𝟏𝟎𝟓 − 𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟒

𝒑𝑩𝟏 = 𝟗. 𝟏𝟏𝟗×𝟏𝟎𝟒 𝑷𝒂 13

13

𝒑𝑩𝟐 = 𝑷 − 𝒑𝑨𝟐 = 𝟏. 𝟎𝟏𝟑𝟐𝟓×𝟏𝟎𝟓 − 𝟎. 𝟓𝟎𝟕×𝟏𝟎𝟒 = 𝟗. 𝟔𝟐𝟓×𝟏𝟎𝟒 𝑷𝒂

𝑷𝑩𝟏 − 𝑷𝑩𝟐
𝑱𝑩 = 𝑫𝑨𝑩
𝑹𝑻 𝒛𝟐 − 𝒛𝟏

'𝟒
𝟗. 𝟏𝟏𝟗×𝟏𝟎𝟒 − 𝟗. 𝟔𝟐𝟓×𝟏𝟎𝟒
𝑱𝑩 = 𝟎. 𝟐𝟑𝟎×𝟏𝟎
𝟖𝟑𝟏𝟒 𝟐𝟗𝟖 𝟎. 𝟏 − 𝟎

𝒎𝒐𝒍 𝑩
𝑱𝑩 = −𝟒. 𝟕𝟎×𝟏𝟎'𝟕
𝒔. 𝒎𝟐

The negative value for 𝑱𝑩 means the flux from point 2 to point 1.

14

14

7
 11/03/2024

STEADY STATE MOLECULAR DIFFUSION IN FLUIDS

• A general expression for flux 𝑵𝑨 will consider the whole fluid moving
in bulk with its average molar velocity and its diffusional flux.
• The molar flux 𝑵𝑨 can be expressed as the sum of molar average
velocity and diffusional flux (JA).
𝝏𝑪𝑨
𝑵𝑨 = 𝑵𝑨 + 𝑵𝑩 𝒙𝑨 − 𝑫𝑨𝑩
𝝏𝒛

For steady state molecular diffusion between two gases A and B, the
net flux is given by:
𝑵 = 𝑵𝑨 + 𝑵𝑩
𝑪𝑨 𝝏𝑪𝑨 𝑪𝑨
𝑵𝑨 = 𝑵𝑨 + 𝑵𝑩 − 𝑫𝑨𝑩 , 𝒔𝒊𝒏𝒄𝒆 𝒙𝑨 =
𝑪 𝝏𝒛 𝑪 15

15

Rearranging and integrating:

𝑪𝑨𝟐 𝒁𝟐
−𝒅𝑪𝑨 𝟏
6 = 6 𝒅𝒁
𝑪𝑨𝟏 𝑵𝑨 𝑪 − 𝑪𝑨 𝑵𝑨 + 𝑵𝑩 𝑪𝑫𝑨𝑩 𝒁𝟏

𝑵
𝑪𝑫𝑨𝑩 𝑪 𝑵 +𝑨𝑵 𝑵𝑨
𝑨 𝑩
𝒍𝒏 𝑪𝑨𝟐 − −𝑪 = 𝒁𝟐 − 𝒁𝟏 = 𝒁
𝑵𝑨 + 𝑵𝑩 𝑪𝑨𝟏 𝑵𝑨 + 𝑵𝑩

or 𝑵𝑨 𝑪𝑨𝟐
𝑵𝑨 𝑪𝑫𝑨𝑩 𝑵𝑨 + 𝑵𝑩 − 𝑪
𝑵𝑨 = 𝒍𝒏 𝑬𝒒(𝟏)
𝑵𝑨 + 𝑵𝑩 𝒁 𝑵𝑨 𝑪𝑨𝟏
𝑵𝑨 + 𝑵𝑩 − 𝑪
16

16

8
 11/03/2024

Molecular Diffusion in Gases

It is more convenient to use ideal gas law for gaseous mixtures. Hence,

𝑪 𝑨 𝑷𝑨
= = 𝒚𝑨
𝑪 𝑷𝒕
𝑷𝑨 is the partial pressure of component A.
𝑷𝒕 is the total pressure.
𝒚𝑨 is mole fraction of component A.

𝑷𝒕 𝑽 = 𝒏𝑹𝑻
𝒏 𝑷𝒕
=𝑪= 𝑬𝒒(𝟐)
𝑽 𝑹𝑻
17

17

Substituting Eq (2) in Eq (1):

𝑵𝑨
𝑵𝑨 𝑷𝒕 𝑷 − 𝒑𝑨𝟐
𝑵𝑨 + 𝑵𝑩 𝒕
𝑵𝑨 = 𝑫𝑨𝑩 𝒍𝒏 𝑬𝒒(𝟑)
𝑵𝑨 + 𝑵𝑩 𝑹𝑻𝒁 𝑵𝑨
𝑷 − 𝒑𝑨𝟏
𝑵𝑨 + 𝑵𝑩 𝒕
or
𝑵𝑨
𝑵𝑨 𝑷𝒕 − 𝒚𝑨𝟐
𝑵𝑨 + 𝑵𝑩
𝑵𝑨 = 𝑫𝑨𝑩 𝒍𝒏
𝑵𝑨 + 𝑵𝑩 𝑹𝑻𝒁 𝑵𝑨
𝑵𝑨 + 𝑵𝑩 − 𝒚𝑨𝟏

18

18

9
 11/03/2024

Case 1—Steady state diffusion of gas A through a stagnant gas B

In this case, 𝑵𝑨 = constant and 𝑵𝑩 = 0.

𝑵𝑨
=𝟏 𝑬𝒒(𝟒)
𝑵𝑨 + 𝑵𝑩

19

19

Substituting Eq (4) in Eq (3):

𝑫𝑨𝑩 𝑷𝒕 𝑷𝒕 − 𝒑𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝑹𝑻𝒁 𝑷𝒕 − 𝒑𝑨𝟏

Since 𝑷𝒕 − 𝒑𝑨𝟐 = 𝒑𝑩𝟐 , 𝑷𝒕 − 𝒑𝑨𝟏 = 𝒑𝑩𝟏 , 𝑷𝑩𝟐 − 𝒑𝑩𝟏 = 𝑷𝑨𝟏 − 𝒑𝑨𝟐 , 𝐭𝐡𝐞𝐧:
𝑫𝑨𝑩 𝑷𝒕 𝑷𝑨𝟏 − 𝒑𝑨𝟐 𝒑𝑩𝟐
𝑵𝑨 = 𝒍𝒏 𝒍𝒏
𝑹𝑻𝒁 𝑷𝑩𝟐 − 𝒑𝑩𝟏 𝒑𝑩𝟏

𝑷𝑩𝟐 − 𝒑𝑩𝟏
𝑷𝑩,𝑴 = 𝒑
𝒍𝒏 𝒑𝑩𝟐
𝑩𝟏

20

20

10
 11/03/2024

Then: 𝑫𝑨𝑩 𝑷𝒕
𝑵𝑨 = 𝑷𝑨𝟏 − 𝒑𝑨𝟐 𝑬𝒒(𝟓)
𝑹𝑻𝒁 𝑷𝑩,𝑴
𝑫𝑨𝑩 𝑷𝒕 𝟏 − 𝒚𝑨𝟐
Or: 𝑵𝑨 = 𝒍𝒏
𝑹𝑻𝒁 𝟏 − 𝒚𝑨𝟏

21

21

Example 3
The diffusivity of carbon tetrachloride, CCl4 through oxygen O2, was
determined in a steady state Arnold evaporating cell.
The cell, having a cross sectional area of
0.82 cm2, was operated at 273 K and 755
mmHg pressure. The average length of
the diffusion path was 17.1 cm.
If 0.0208 cc of CCl4 was evaporated
in 10 hours of steady state operation,
what should be the value of the
diffusivity of CCl4 through oxygen?

22

11
 11/03/2024

Solution
Vapour pressure of CCl4 at 273 K = 33 mm Hg
Density of liquid CCl4 = 1.59 g/cm3
Molecular weight of CCl4 = 154 g/mol
Considering O2 to be non-diffusing and with T = 273 K, Pt = 755 mm Hg,
Z = 17.1 cm.
0.0208 cc of CCl4 is evaporating in 10 hours.
𝟎. 𝟎𝟐𝟎𝟖 𝒄𝒄 𝟏. 𝟓𝟗𝒈 𝒎𝒐𝒍
𝑹𝒂𝒕𝒆 𝒐𝒇 𝒆𝒗𝒂𝒑𝒐𝒓𝒂𝒕𝒊𝒐𝒏 = × = 𝟐. 𝟏𝟒𝟓×𝟏𝟎!𝟓 𝒎𝒐𝒍/𝒉
𝟏𝟎 𝒉 𝒄𝒄 𝟏𝟓𝟒𝒈

𝑹𝒂𝒕𝒆 𝒐𝒇 𝒆𝒗𝒂𝒑𝒐𝒓𝒂𝒕𝒊𝒐𝒏 𝟐. 𝟏𝟒𝟓×𝟏𝟎$𝟓 𝒎𝒐𝒍/𝒉 𝟏𝒉 𝒎𝒐𝒍

𝑵𝑨 = = $𝟒 𝟐
× = 𝟕. 𝟐𝟕×𝟏𝟎$𝟖 𝟐
𝑪𝒓𝒐𝒔𝒔 𝒔𝒆𝒄𝒕𝒊𝒐𝒏𝒂𝒍 𝒂𝒓𝒆𝒂 𝟎. 𝟖𝟐×𝟏𝟎 𝒎 𝟑𝟔𝟎𝟎 𝒔 𝒎 .𝑺
23

23

𝑫𝑨𝑩 𝑷𝒕 𝑷𝒕 − 𝒑𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝑹𝑻𝒁 𝑷𝒕 − 𝒑𝑨𝟏

𝑵𝑨 ×𝑹×𝑻×𝒁
𝑫𝑨𝑩 =
𝑷 − 𝒑𝑨𝟐
𝑷𝒕 𝒍𝒏 𝒕
𝑷𝒕 − 𝒑𝑨𝟏

×𝟖𝟑𝟏𝟒×𝟐𝟕𝟑×𝟏𝟕. 𝟏×𝟏𝟎'𝟐
𝟕. 𝟐𝟕×𝟏𝟎$𝟖
𝑫𝑨𝑩 =
𝟕𝟓𝟓
𝟕𝟓𝟓 𝟕𝟔𝟎 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓 − 𝟎
𝟓
𝟕𝟔𝟎 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎 𝒍𝒏
𝟕𝟓𝟓 𝟓 − 𝟑𝟑 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓
𝟕𝟔𝟎 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎 𝟕𝟔𝟎

𝑫𝑨𝑩 = 𝟔. 𝟑𝟓𝟓×𝟏𝟎'𝟔 𝒎𝟐 /𝒔
24

24

12
 11/03/2024

Case 2—Equimolar counter diffusion

In this case, 𝑵𝑨 = −𝑵𝑩

Hence, we can consider the general expression for flux as:

𝝏𝑪𝑨
𝑵𝑨 = 𝑵𝑨 + 𝑵𝑩 𝒙𝑨 − 𝑫𝑨𝑩
𝝏𝒁

25

25

𝝏𝑪𝑨
Integrating: 𝑵𝑨 = −𝑫𝑨𝑩
𝝏𝒁

𝒁𝟐 𝑪𝑨𝟐
𝑵𝑨 6 𝒅𝒁 = −𝑫𝑨𝑩 6 𝒅𝑪𝑨
𝒁𝟏 𝑪𝑨𝟏

−𝑫𝑨𝑩
𝑵𝑨 = 𝑪𝑨𝟐 − 𝑪𝑨𝟏 𝒘𝒉𝒆𝒓𝒆 𝒁 = 𝒁𝟐 − 𝒁𝟏
𝒁

𝑫𝑨𝑩
𝑵𝑨 = 𝒑𝑨𝟐 − 𝒑𝑨𝟏 𝑬𝒒(𝟔)
𝑹𝑻𝒁

26

26

13
 11/03/2024

Case 3—Steady state diffusion in multicomponent mixtures

For multicomponent mixtures, effective diffusivity (𝑫𝑨,𝑴 )can be
determined by using:
𝑵𝑨 − 𝒚𝑨 ∑𝒏𝒊7𝑨 𝑵𝒊
𝑫𝑨,𝑴 =
𝟏
∑𝒏𝒊7𝑨 𝒚 𝑵 − 𝒚𝑨 𝑵𝒊
𝑫𝑨𝒊 𝒊 𝑨

𝑫𝑨𝒊 are the binary diffusivities.

𝑫𝑨,𝑴 may vary considerably from one end of the diffusion path to the
other, but a linear variation with distance can be assumed.

27

27

For this situation, assume all but one component is stagnant, then,
𝟏 − 𝒚𝑨 𝟏
𝑫𝑨,𝑴 = 𝒚 = 𝒚
∑𝒏𝒊7𝑩 𝒊 ∑𝒏𝒊7𝑩 𝒊
𝑫𝑨𝒊 𝑫𝑨𝒊

where 𝒚𝒊 is the mole fraction of component i on an A-free basis.

Substituting 𝑫𝑨,𝑴 instead of 𝑫𝑨,𝑩 in Eqs (5) and (6), the mass transfer
rate for multicomponent mixtures can be determined.
𝑫𝑨𝑩 𝑷𝒕
𝑵𝑨 = 𝑷𝑨𝟏 − 𝒑𝑨𝟐 𝑬𝒒(𝟓)
𝑹𝑻𝒁 𝑷𝑩,𝑴
𝑫𝑨𝑩
𝑵𝑨 = 𝒑𝑨𝟐 − 𝒑𝑨𝟏 𝑬𝒒(𝟔)
𝑹𝑻𝒁 28

28

14
 11/03/2024

Diffusivity Prediction in Gases

• Diffusion coefficient depends on temperature, pressure and composition
of the components.

• Diffusivity can be
determined
experimentally.

29

29

In some cases, it is very difficult to determine experimentally.

Hirschfelder-Bird-Spotz developed an empirical relation to determine the
diffusivity for mixtures of non-polar or a polar with non-polar gas.
𝟏 𝟏 𝟏 𝟏
𝟏𝟎'𝟒 𝟏. 𝟎𝟖𝟒 − 𝟎. 𝟐𝟒𝟗 𝑴𝑨 𝑴𝑩 𝑻
+ 𝟑/𝟐
+
𝑴𝑨 𝑴𝑩
𝑫𝑨𝑩 =
𝑲𝑻
𝑷𝒕 𝒓𝑨𝑩 𝟐 𝒇
𝜺𝑨𝑩
𝑫𝑨𝑩 is the diffusivity, m2/s
T is the absolute temperature, K
𝑴𝑨 , 𝑴𝑩 is the molecular weight of A and B respectively, kg/kmol.
𝑷𝒕 is the absolute pressure, N/m2
30

30

15
 11/03/2024

𝒓𝑨 ;𝒓𝑩
𝒓𝑨𝑩 is the molecular separation at collision = , nm
𝟐
𝜺𝑨𝑩 is the energy of molecular attraction 𝜺𝑨𝑩 = 𝜺𝑨 𝜺𝑩
K is the Boltzmann’s constant.
𝑲𝑻
𝒇 is the collision function given by Fig. 2.1
𝜺𝑨𝑩
The values of r and 𝜺 such as those listed in Table 2.2 can be
calculated from other properties of gases such as viscosity.
They can also be estimated empirically by:

𝒓 = 𝟏. 𝟏𝟖𝒗𝟏/𝟑 𝜺b = 𝟏. 𝟐𝟏𝑻
𝑲 𝒃

where v is the molal volume of liquid at normal boiling point,

m3/kmol and 𝑻𝒃 is the normal boiling point, K.
31

31

32

32

16
 11/03/2024

33

33

Example 4
Estimate the diffusivities of the following gas mixtures:
(a) Nitrogen—carbon dioxide, 1 Standard atm., 25ºC.
(b) Hydrogen chloride—air, 200 kN/m2, 25ºC.

Solution
(a) Nitrogen—carbon dioxide, 1 Standard atm., 25ºC.
Let A denote nitrogen and B denote carbon dioxide, from Table 2.2:
𝒓𝑨 = 𝟎. 𝟑𝟕𝟗𝟖 𝒏𝒎
𝒓𝑩 = 𝟎. 𝟑𝟗𝟒𝟏 𝒏𝒎

𝟎. 𝟑𝟕𝟗𝟖 + 𝟎. 𝟑𝟗𝟒𝟏
𝒓𝑨𝑩 = = 𝟎. 𝟑𝟖𝟔𝟗𝟓 𝒏𝒎
𝟐 34

34

17
 11/03/2024

𝜺
= 𝟕𝟏. 𝟔
𝑲 𝑨

𝜺
= 𝟏𝟗𝟓. 𝟐
𝑲 𝑩

𝜺
= 𝟕𝟏. 𝟔 ×𝟏𝟗𝟓. 𝟐 = 𝟏𝟏𝟖. 𝟎𝟓𝟔
𝑲 𝑨𝑩

𝑲𝑻 𝟐𝟗𝟖
= = 𝟐. 𝟓𝟐
𝜺𝑨𝑩 𝟏𝟏𝟖. 𝟎𝟓𝟔

35

35

𝑲𝑻
𝒇 = 𝟎. 𝟓
𝜺𝑨𝑩

𝟏 𝟏 𝟏 𝟏
+ = + = 𝟎. 𝟐𝟒𝟐
𝑴𝑨 𝑴𝑩 𝟐𝟖 𝟒𝟒

36

36

18
 11/03/2024

𝟏 𝟏 𝟏 𝟏
𝟏𝟎'𝟒 𝟏. 𝟎𝟖𝟒 − 𝟎. 𝟐𝟒𝟗 𝑴𝑨 𝑴𝑩 𝑻
+ 𝟑/𝟐
+
𝑴𝑨 𝑴𝑩
𝑫𝑨𝑩 =
𝑲𝑻
𝑷𝒕 𝒓𝑨𝑩 𝟐 𝒇
𝜺𝑨𝑩

𝟏𝟎'𝟒 𝟏. 𝟎𝟖𝟒 − 𝟎. 𝟐𝟒𝟗×𝟎. 𝟐𝟒𝟐 × 𝟐𝟗𝟖 𝟑/𝟐 × 𝟎. 𝟐𝟒𝟐

𝑫𝑨𝑩 =
𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓 × 𝟎. 𝟑𝟖𝟔𝟗𝟓 𝟐 ×𝟎. 𝟓

𝑫𝑨𝑩 = 𝟏. 𝟔𝟖𝟎𝟓×𝟏𝟎'𝟓 𝒎𝟐 /𝒔

37

37

b) Hydrogen chloride—air, 200 kN/m2, 25ºC.

Let A denote HCl and B denote Air, from Table 2.2:
𝒓𝑨 = 𝟎. 𝟑𝟑𝟑𝟗 𝒏𝒎 𝒓𝑩 = 𝟎. 𝟑𝟕𝟏𝟏 𝒏𝒎
𝟎. 𝟑𝟑𝟑𝟗 + 𝟎. 𝟑𝟕𝟏𝟏
𝒓𝑨𝑩 = = 𝟎. 𝟑𝟓𝟐𝟓 𝒏𝒎
𝟐
𝜺 𝜺
= 𝟑𝟒𝟒. 𝟕 = 𝟕𝟖. 𝟔
𝑲 𝑨 𝑲 𝑩
𝜺
= 𝟑𝟒𝟒. 𝟕 ×𝟕𝟖. 𝟔 = 𝟏𝟔𝟒. 𝟔
𝑲 𝑨𝑩

𝑲𝑻 𝟐𝟗𝟖
= = 𝟏. 𝟖𝟏
𝜺𝑨𝑩 𝟏𝟔𝟒. 𝟔
38

38

19
 11/03/2024

𝑲𝑻
𝒇 = 𝟎. 𝟔𝟐
𝜺𝑨𝑩

𝟏 𝟏 𝟏 𝟏
+ = + = 𝟎. 𝟐𝟒𝟗
𝑴𝑨 𝑴𝑩 𝟑𝟔. 𝟓 𝟐𝟗

𝟏 𝟏 𝟏 𝟏
𝟏𝟎'𝟒 𝟏. 𝟎𝟖𝟒 − 𝟎. 𝟐𝟒𝟗 𝑴𝑨 𝑴𝑩 𝑻
+ 𝟑/𝟐
+
𝑴𝑨 𝑴𝑩
𝑫𝑨𝑩 =
𝑲𝑻
𝑷𝒕 𝒓𝑨𝑩 𝟐 𝒇 𝜺
𝑨𝑩
𝟏𝟎'𝟒 𝟏. 𝟎𝟖𝟒 − 𝟎. 𝟐𝟒𝟗× 𝟎. 𝟐𝟒𝟗 × 𝟐𝟗𝟖 𝟑/𝟐 × 𝟎. 𝟐𝟒𝟗
𝑫𝑨𝑩 =
𝟐𝟎𝟎×𝟏𝟎𝟑 × 𝟎. 𝟑𝟓𝟐𝟓 𝟐 ×𝟎. 𝟔𝟐

𝑫𝑨𝑩 = 𝟖. 𝟒𝟗𝟔×𝟏𝟎'𝟔 𝒎𝟐 /𝒔 39

39

Molecular Diffusion in Liquids

In the case of diffusion in liquids, C and 𝑫𝑨𝑩 may vary considerably with
respect to process conditions. Hence,
𝑵𝑨
𝑵𝑨 𝑫𝑨𝑩 𝝆 − 𝒙𝑨𝟐
𝑵𝑨 + 𝑵𝑩
𝑵𝑨 = 𝒍𝒏
𝑵𝑨 + 𝑵𝑩 𝒁 𝑴 𝒂𝒗 𝑵𝑨
− 𝒙𝑨𝟏
𝑵𝑨 + 𝑵𝑩

where 𝝆 is solution density and M is solution molecular weight.

Case 1—Diffusion of liquid A through a stagnant liquid B
In this case, 𝑵𝑨 = constant and 𝑵𝑩 = 0.
𝑫𝑨𝑩 𝝆
𝑵𝑨 = 𝒙𝑨𝟏 − 𝒙𝑨𝟐
𝒁𝒙𝑨,𝑴 𝑴 𝒂𝒗
40

40

20
 11/03/2024

where 𝒙𝑩𝟐 − 𝒙𝑩𝟏

𝒙𝑩,𝑴 = 𝒙
𝒍𝒏 𝒙𝑩𝟐
𝑩𝟏

𝑫𝑨𝑩 𝝆 𝟏 − 𝒙𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝒁 𝑴 𝒂𝒗 𝟏 − 𝒙𝑨𝟏

41

41

Example 5
Crystal of copper sulphate CuSO4.5H2O falls through a large tank of pure
water at 20ºC. Estimate the rate at which the crystal dissolves by calculating
the flux of CuSO4 from the crystal surface to the bulk solution. Molecular
diffusion occurs through a film of water uniformly 0.0305 mm thick
surrounding the crystal. At the inner side of the film, adjacent to the crystal
surface, the concentration of CuSO4 is 0.0229 mole fraction CuSO4
(solution density = 1193 kg/m3). The outer surface of the film is pure water.
The diffusivity of CuSO4 is 7.29 10–10 m2/s. Temperature = 293 K.
Molecular weight of CuSO4= 160 g/mol.

42

42

21
 11/03/2024

Solution
𝒁 = 𝟎. 𝟎𝟑𝟎𝟓 × 𝟏𝟎'𝟑 m

∑ 𝒚𝒊 ×𝑴𝒊 𝟎. 𝟎𝟐𝟐𝟗×𝟏𝟔𝟎 + 𝟎. 𝟗𝟕𝟕𝟏×𝟏𝟖

𝑴𝒂𝒗 = = = 𝟐𝟏. 𝟐𝟓𝟏𝟖 𝒈/𝒎𝒐𝒍
∑ 𝒚𝒊 𝟏
𝝆 𝟏𝟏𝟗𝟑
= = 𝟓𝟖. 𝟏𝟑𝟔 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑴 𝟐𝟏. 𝟐𝟓𝟏𝟖
For pure water,
𝝆 𝟏𝟎𝟎𝟎
= = 𝟓𝟓. 𝟔𝟓 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑴 𝟐 𝟏𝟖

𝝆 𝟓𝟖. 𝟏𝟑𝟔 + 𝟓𝟓. 𝟔𝟓

= = 𝟓𝟔. 𝟖𝟒𝟖𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑴 𝒂𝒗 𝟐
43

43

𝑫𝑨𝑩 = 𝟕. 𝟐𝟗×𝟏𝟎'𝟏𝟎 𝒎𝟐 /𝒔

Assuming water to be non-diffusing

𝑫𝑨𝑩 𝝆 𝟏 − 𝒙𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝒁 𝑴 𝒂𝒗 𝟏 − 𝒙𝑨𝟏

𝟕. 𝟐𝟗×𝟏𝟎'𝟏𝟎 𝟏−𝟎
𝑵𝑨 = ×𝟓𝟔. 𝟖𝟒𝟖×𝒍𝒏
𝟎. 𝟎𝟑𝟎𝟓×𝟏𝟎'𝟑 𝟏 − 𝟎. 𝟎𝟐𝟐𝟗

𝑵𝑨 = 𝟑. 𝟏𝟓×𝟏𝟎'𝟓 𝒎𝒐𝒍/𝒎𝟐 . 𝒔

44

44

22
 11/03/2024

Case 2—Equimolar counter-diffusion

In this case, 𝑵𝑨 = -𝑵𝑩 .

𝑫𝑨𝑩 𝑫𝑨𝑩 𝝆
𝑵𝑨 = 𝑪𝑨𝟏 − 𝑪𝑨𝟐 = 𝒙𝑨𝟏 − 𝒙𝑨𝟐
𝒁 𝒁 𝑴 𝒂𝒗

45

45

Diffusivity Prediction in Liquids

46

46

23
 11/03/2024

For some cases such as dilute solution of non-electrolytes, the diffusivity

can be estimated by using Wilke and Chang empirical correlation.
𝟏𝟏𝟕. 𝟑×𝟏𝟎'𝟏𝟖 𝝋𝑴𝑩 𝟎.𝟓
𝑻
𝑫𝑨𝑩 =
𝝁𝒗𝟎.𝟔
𝑨
𝑫𝑨𝑩 is the diffusivity of A in very dilute solution in solvent B, m2/s
𝑴𝑩 is the molecular weight of solvent, kg/kmol.
T is the absolute temperature, K
𝝁 is the solution viscosity, kg/m-s

𝒗𝑨 is the solute molal volume at normal boiling point, m3/kmol.

= 0.0756 for water as solute.
47

47

𝝋 is the association factor for solvent.

= 2.26 for water as solvent
= 1.90 for methanol as solvent
= 1.50 for ethanol as solvent
= 1.00 for unassociated solvents, e.g. benzene and ethyl ether.

48

48

24
 11/03/2024

49

49

Example 6
Estimate the diffusivity of isoamyl alcohol (C5H12O) at infinite dilution
in water at 288 K.
Solution
Viscosity of water = 1.145 cp
𝑽𝑨 (𝒃𝒚 𝑲𝒐𝒑𝒑’𝒔 𝒍𝒂𝒘) = 𝟓𝑽𝑪 + 𝟏𝟐𝑽𝑯 + 𝟏𝑽𝑶

𝑽𝑨 = 𝟓×𝟎. 𝟎𝟏𝟒𝟖 + 𝟏𝟐×𝟎. 𝟎𝟎𝟑𝟕 + 𝟏×𝟎. 𝟎𝟎𝟕𝟒

𝑽𝑨 = 𝟎. 𝟏𝟐𝟓𝟖 𝒎𝟑 /𝒌𝒎𝒐𝒍

𝝋 = 2.26

50

50

25
 11/03/2024

𝟏𝟏𝟕. 𝟑×𝟏𝟎'𝟏𝟖 𝝋𝑴𝑩 𝟎.𝟓

𝑻
𝑫𝑨𝑩 =
𝝁𝒗𝟎.𝟔
𝑨

𝟏𝟏𝟕. 𝟑×𝟏𝟎'𝟏𝟖 𝟐. 𝟐𝟔×𝟏𝟖 𝟎.𝟓 ×𝟐𝟖𝟖

𝑫𝑨𝑩 =
𝟎. 𝟎𝟎𝟏𝟏𝟒𝟓 × 𝟎. 𝟏𝟐𝟓𝟖 𝟎.𝟔

𝑫𝑨𝑩 = 𝟎. 𝟔𝟓𝟑×𝟏𝟎'𝟗 𝒎𝟐 /𝒔

51

51

Pseudo Steady State Diffusion

• In many mass transfer operations, one of the boundaries between the
fluids may move with time.
• If the length of the diffusion path changes over a period of time, a
pseudo steady state develops.
𝒅𝒁
𝑵𝑨𝒁 = ×𝑪𝑨,𝑳
𝒅𝒕
𝑪𝑫𝑨𝑩 𝒅𝒁
𝑵𝑨𝒁 = × 𝒙𝑩𝟐 − 𝒙𝑩𝟏 = ×𝑪𝑨,𝑳
𝒁𝒙𝑩𝑴 𝒅𝒕

Integrating between t = 0, Z = Zt0 and t = t, Z = Zt

52

52

26
 11/03/2024

𝒁𝒕 𝒕
𝑪𝑫𝑨𝑩 𝒙𝑩𝟐 − 𝒙𝑩𝟏
j 𝒛𝒅𝒛 = 6 𝒅𝒕
𝒙𝑩𝑴 𝑪𝑨,𝑳 𝟎
𝒁𝒕𝟎

After integration and simplification,

𝒕 𝒙𝑩𝑴 𝑪𝑨,𝑳 𝒁𝒕 + 𝒁𝒕𝟎
=
𝒁𝒕 − 𝒁𝒕𝟎 𝟐𝑪𝑫𝑨𝑩 𝒙𝑨𝟏 − 𝒙𝑨𝟐

𝒕 𝒙𝑩𝑴 𝑪𝑨,𝑳 𝒁𝒕 + 𝒁𝒕𝟎 + 𝒁𝒕𝟎 − 𝒁𝒕𝟎

=
𝒁𝒕 − 𝒁𝒕𝟎 𝟐𝑪𝑫𝑨𝑩 𝒙𝑨𝟏 − 𝒙𝑨𝟐

𝒕 𝒙𝑩𝑴 𝑪𝑨,𝑳 𝒁𝒕 − 𝒁𝒕𝟎 𝟐𝒁𝒕𝟎 𝒙𝑩𝑴 𝑪𝑨,𝑳

= + , 𝑬𝒒(𝟕)
𝒁𝒕 − 𝒁𝒕𝟎 𝟐𝑪𝑫𝑨𝑩 𝒙𝑨𝟏 − 𝒙𝑨𝟐 𝟐𝑪𝑫𝑨𝑩 𝒙𝑨𝟏 − 𝒙𝑨𝟐
53

53

Equation (7) is of the form, 𝒚 = 𝒎𝒙 + 𝑪

𝒕
𝒚=
𝒁𝒕 − 𝒁𝒕𝟎
𝒙 = 𝒁𝒕 − 𝒁𝒕𝟎
𝒙𝑩𝑴 𝑪𝑨,𝑳
𝑺𝒍𝒐𝒑𝒆, 𝒎 =
𝟐𝑪𝑫𝑨𝑩 𝒙𝑨𝟏 − 𝒙𝑨𝟐
𝒁𝒕𝟎 𝒙𝑩𝑴 𝑪𝑨,𝑳
𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕, 𝑪 =
𝟐𝑪𝑫𝑨𝑩 𝒙𝑨𝟏 − 𝒙𝑨𝟐
𝒕
Plotting 𝒁 '𝒁 against 𝒁𝒕 − 𝒁𝒕𝟎 , from the slope of line, 𝑫𝑨𝑩 can be
𝒕 𝒕𝟎
calculated.

• This equation is called as Winkelmann’s relation. 54

54

27
 11/03/2024

DIFFUSION IN SOLIDS
• The rate of diffusion of substance A per unit cross section of solid is
proportional to the concentration gradient in the direction of diffusion.
𝒅𝑪𝑨
𝑵𝑨𝒁 = −𝑫𝑨
𝒅𝒛

𝑫𝑨 is the diffusivity of A through the solid.

When the diffusion is taking place through a flat slab of thickness Z,

then: 𝑫𝑨 𝑪𝑨𝟏 − 𝑪𝑨𝟐
𝑵𝑨𝒁 =
𝒁

𝑪𝑨𝟏 𝒂𝒏𝒅 𝑪𝑨𝟐 are concentrations at opposite sides of the slab.

55

55

𝑫𝑨 𝑺𝒂𝒗 𝑪𝑨𝟏 − 𝑪𝑨𝟐

𝑾 = 𝑵𝑨 𝑺𝒂𝒗 =
𝒁
𝑺𝒂𝒗 is average mass transfer area of respective solid surfaces.

For radial diffusion through a solid cylinder of inner and outer radii r1
and r2 respectively and its length l,
𝑺𝒂𝒗 = 𝟐𝝅𝒓𝒍
𝒅𝑪
𝑾 = −𝑫𝑨 𝟐𝝅𝒓𝒍
𝒅𝒓
On integrating:
𝒓𝟐 𝑪𝑨𝟐
𝒅𝒓
𝑾6 = −𝑫𝑨 𝟐𝝅𝒍 6 𝒅𝑪
𝒓𝟏 𝒓 𝑪𝑨𝟏
56

56

28
 11/03/2024

𝒓𝟐
𝑾𝒍𝒏 = −𝑫𝑨 𝟐𝝅𝒍 𝑪𝑨𝟐 − 𝑪𝑨𝟏
𝒓𝟏

𝑫𝑨 𝟐𝝅𝒍 𝑪𝑨𝟏 − 𝑪𝑨𝟐 𝒓𝟐 − 𝒓𝟏

𝑾= 𝒓
𝒍𝒏 𝟐 𝒓𝟐 − 𝒓𝟏
𝒓𝟏

𝑫𝑨 𝑺𝒂𝒗 𝑪𝑨𝟏 − 𝑪𝑨𝟐

𝑾=
𝒁
𝟐𝝅𝒍 𝒓𝟐 − 𝒓𝟏 𝒁 = 𝒓𝟐 − 𝒓𝟏
𝑺𝒂𝒗 = 𝒓
𝒍𝒏 𝒓𝟐
𝟏

Similarly for radial diffusion through a spherical shell of inner and

outer radii 𝒓𝟏 and 𝒓𝟐 , the surface is
𝑺𝒂𝒗 = 𝟒𝝅𝒓𝟐 𝒓𝟏 𝒁 = 𝒓𝟐 − 𝒓𝟏 57

57

Molecular diffusion in solid

Diffusion in solids following Fick’s law
Derivation of equations:
𝒅𝒙𝑨 𝒄𝑨
𝑵𝑨 = −𝒄𝑫𝑨𝑩 + 𝑵𝑨 + 𝑵𝑩
𝒅𝒛 𝒄
𝒄𝑨
The bulk flow term, 𝒄
𝑵𝑨 + 𝑵𝑩 , even if present, is usually small, since
𝒄𝑨
𝒄
or 𝒙𝑨 is quite small. Hence, it is neglected. Also, c is assumed constant
giving for diffusion in solids,
𝒅𝒄𝑨
𝑵𝑨 = −𝑫𝑨𝑩 𝑫𝑨𝑩 ≠ 𝑫𝑩𝑨
𝒅𝒛

𝑫𝑨𝑩 𝒄𝑨𝟏 − 𝒄𝑨𝟐

𝑵𝑨 =
𝒛𝟐 − 𝒛𝟏
58

29
 11/03/2024

For the case of diffusion radially through a cylinder wall of inner radius
r1 and outer radius r2 and length L,
o𝑨
𝑵 𝒅𝒄𝑨
= −𝑫𝑨𝑩
𝟐𝝅𝒓𝑳 𝒅𝒓
𝟐𝝅𝑳
o 𝑨 = 𝑫𝑨𝑩 𝒄𝑨𝟏 − 𝒄𝑨𝟐
𝑵
𝒍𝒏 𝒓𝟐 ⁄𝒓𝟏

The solubility of a solute gas (A) in a solid is usually expressed as S m3

solute (at STP of 0°C and 1 atm) per m3 of solid per atm partial
pressure of A.
𝒎𝟑 𝑺𝑻𝑷
𝑺 𝟑
𝒄𝑨 = 𝒎 𝒔𝒐𝒍𝒊𝒅. 𝒂𝒕𝒎 = 𝑺𝒑𝑨 𝒎𝒐𝒍 𝑨
𝟑
𝒎 𝑺𝑻𝑷 𝟐𝟐. 𝟒𝟏𝟒 𝒎𝟑 𝒔𝒐𝒍𝒊𝒅
𝟐𝟐. 𝟒𝟏𝟒
𝒎𝒐𝒍 𝑨
59

Example
The gas hydrogen at 17°C and 0.01 atm partial pressure is diffusing
through a membrane of vulcanized neoprene rubber 0.5 mm thick. The
pressure of H2 on the other side of the 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 17°C is 0.051 m3 (at
STP of 0°C and 1 atm)/m3 solid. atm and the diffusivity 𝑫𝑨𝑩 = 𝟏. 𝟎𝟑
×𝟏𝟎'𝟏𝟎 𝒎𝒔 /𝒔 at 17°C.

𝑺𝒑𝑨 𝒎𝒐𝒍 𝑨 𝟎. 𝟎𝟓𝟏 𝟎. 𝟎𝟏𝟎

𝒄𝑨 = =
𝟐𝟐. 𝟒𝟏𝟒 𝒎𝟑 𝒔𝒐𝒍𝒊𝒅 𝟐𝟐. 𝟒𝟏𝟒

𝒎𝒐𝒍
𝒄𝑨 = 𝟐. 𝟐𝟖×𝟏𝟎'𝟓
𝒎𝟑 𝒔𝒐𝒍𝒊𝒅

60

30
 11/03/2024

𝑫𝑨𝑩 𝒄𝑨𝟏 − 𝒄𝑨𝟐

𝑵𝑨 =
𝒛𝟐 − 𝒛𝟏

𝟏. 𝟎𝟑×𝟏𝟎'𝟏𝟎 𝟐. 𝟐𝟖×𝟏𝟎'𝟓 − 𝟎
𝑵𝑨 =
𝟎. 𝟓 − 𝟎 ⁄𝟏𝟎𝟎𝟎

𝒎𝒐𝒍
𝑵𝑨 = 𝟒. 𝟔𝟗×𝟏𝟎'𝟏𝟐
𝒔. 𝒎𝟐

61

Permeability equations for diffusion in solids

In many cases the experimental data for diffusion of gases in solids are
not given as diffusivities and solubilities but as permeabilities, Pm, in m3
of solute gas A at STP (0°C and 1 atm) diffusing per second per m2
cross-sectional area through a solid 1 m thick under pressure difference
of 1 atm pressure. This can be related to Fick’s equation as follow:
𝑫𝑨𝑩 𝒄𝑨𝟏 − 𝒄𝑨𝟐
𝑵𝑨 =
𝒛𝟐 − 𝒛𝟏

𝑺𝒑𝑨𝟏 𝑺𝒑𝑨𝟐
𝒄𝑨𝟏 = 𝒄𝑨𝟐 =
𝟐𝟐. 𝟒𝟏𝟒 𝟐𝟐. 𝟒𝟏𝟒

𝑫𝑨𝑩 𝑺 𝒑𝑨𝟏 − 𝒑𝑨𝟐 𝑷𝑴 𝒑𝑨𝟏 − 𝒑𝑨𝟐

𝑵𝑨 = =
𝟐𝟐. 𝟒𝟏𝟒 𝒛𝟐 − 𝒛𝟏 𝟐𝟐. 𝟒𝟏𝟒 𝒛𝟐 − 𝒛𝟏
62

31
 11/03/2024

Where the permeability Pm is:

𝒎𝟑 (𝑺𝑻𝑷)
𝑷𝒎 = 𝑫𝑨𝑩 𝑺 𝒔.𝒎𝟐 .𝒂𝒕𝒎/𝒎

When there are several solids 1, 2, 3, …., in series and L1, L2, L3, …,
represent the thickness of each then:

𝒑𝑨𝟏 − 𝒑𝑨𝟐 𝟏
𝑵𝑨 =
𝟐𝟐. 𝟒𝟏𝟒 𝑳𝟏 ⁄𝑷𝒎𝟏 +𝑳𝟐 ⁄𝑷𝒎𝟐 + ⋯

Where 𝒑𝑨𝟏 − 𝒑𝑨𝟐 is the overall partial pressure difference.

63

Experimental diffusivities, solubilities, and permeabilities

64

32
 11/03/2024

Example
A polyethylene film 0.00015 m (0.15 mm) thick is being considered for
use in packaging a pharmaceutical product at 30°C. if the partial
pressure of O2 outside is 0.21 atm and inside the package 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.

'𝟏𝟐
𝒎𝟑 (𝑺𝑻𝑷)
𝑷𝒎 = 𝟒. 𝟕×𝟏𝟎
𝒔. 𝒎𝟐 . 𝒂𝒕𝒎/𝒎

𝑷𝑴 𝒑𝑨𝟏 − 𝒑𝑨𝟐
𝑵𝑨 =
𝟐𝟐. 𝟒𝟏𝟒 𝒛𝟐 − 𝒛𝟏

𝟒. 𝟕×𝟏𝟎!𝟏𝟐 𝟎. 𝟐𝟏 − 𝟎. 𝟎𝟏 𝒎𝒐𝒍
𝑵𝑨 = = 𝟐. 𝟒𝟖×𝟏𝟎!𝟏𝟎
𝟐𝟐. 𝟒𝟏𝟒 𝟎. 𝟎𝟎𝟎𝟏𝟓 − 𝟎 𝒔. 𝒎𝟐
65

Diffusion in porous solids that depends on structure

Diffusion of liquid in porous solids

𝜺𝑫𝑨𝑩 𝒄𝑨𝟏 − 𝒄𝑨𝟐

𝑵𝑨 =
𝝉 𝒛𝟐 − 𝒛𝟏

Where 𝜺 is the open void fraction, 𝑫𝑨𝑩 is the

diffusivity of salt in water, and 𝝉 is a factor
which corrects for the path longer than
𝒛𝟐 − 𝒛𝟏 .

For inert type solid 𝝉 can vary from 1.5 to 5.

𝜺
𝑫𝑨 𝒆𝒇𝒇 = 𝑫𝑨𝑩
𝝉
66

33
 11/03/2024

Example
A sintered solid of silica 2 mm thick is porous with a void fraction 𝜺 of
0.3 and tortuosity 𝝉 of 4. The pores are filled with water at 298K. At one
face the concentration of KCl if held at 0.1 gmol/L, and fresh water
flows rapidly by the other face. Neglecting any other resistances but that
in the porous solid, calculate the diffusion of KCl at steady state.
𝑫𝑨𝑩 = 𝟏. 𝟖𝟕×𝟏𝟎'𝟗 𝒎𝟐 /𝒔
𝟎. 𝟏 𝒎𝒐𝒍
𝒄𝑨𝟏 = = 𝟏. 𝟎×𝟏𝟎'𝟒 = 𝟎. 𝟏 𝒎𝒐𝒍/𝒎𝟑
𝟏𝟎𝟎𝟎 𝑳
𝒄𝑨𝟐 = 𝟎
𝜺𝑫𝑨𝑩 𝒄𝑨𝟏 − 𝒄𝑨𝟐 𝟎. 𝟑 𝟏. 𝟖𝟕×𝟏𝟎!𝟗 𝟎. 𝟏 − 𝟎
𝑵𝑨 = =
𝝉 𝒛𝟐 − 𝒛𝟏 𝟒 𝟎. 𝟎𝟎𝟐 − 𝟎
𝒎𝒐𝒍
𝑵𝑨 = 𝟕. 𝟎𝟏×𝟏𝟎!𝟗
𝒔. 𝒎𝟐
67

Diffusion of gases in porous solids

𝜺𝑫𝑨𝑩 𝒄𝑨𝟏 − 𝒄𝑨𝟐

𝑵𝑨 =
𝝉 𝒛𝟐 − 𝒛𝟏

𝜺𝑫𝑨𝑩 𝒑𝑨𝟏 − 𝒑𝑨𝟐

𝑵𝑨 =
𝝉𝑹𝑻 𝒛𝟐 − 𝒛𝟏

The value of tortuosity 𝝉 must be determined experimentally.

Diffusion is assumed to occur only through the voids or pores and not
through the actual solid particles.

68

34
 11/03/2024

Example 7
Alcohol vapour is diffusing through a layer of water vapour under
equimolar counter diffusion at 35ºC and 1 atm. pressure. The molal
concentration of alcohol on the two sides of the gas film (water vapour) 0.3
mm thick are 80% and 10% respectively. Assuming the diffusivity of
alcohol–water vapour to be 0.18 cm2/s, (i) calculate the rate of diffusion of
alcohol and water vapour in kg/hr through an area of 100 cm2 (ii) if the
water vapour layer is stagnant, estimate the rate of diffusion of alcohol
vapour.

69

69

Solution
(i) Equimolar counter diffusion
T = (273 + 35) = 308 K, Pt = 1 atm
𝟒𝟔𝒌𝒈
Z = 0.3 mm 𝑫𝑨𝑩 = 𝟎. 𝟏𝟖×𝟏𝟎 '𝟒 𝟐
𝒎 /𝒔 𝑴𝒘𝒆𝒕𝒉𝒂𝒏𝒐𝒍 =
𝒎𝒐𝒍
𝑫𝑨𝑩
𝑵𝑨 = 𝒑𝑨𝟏 − 𝒑𝑨𝟐
𝑹𝑻𝒁

𝑫𝑨𝑩 ×𝑷𝒕
𝑵𝑨 = 𝒚𝑨𝟏 − 𝒚𝑨𝟐
𝑹𝑻𝒁
𝟎. 𝟏𝟖×𝟏𝟎'𝟒 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓
𝑵𝑨 = 𝟎. 𝟖 − 𝟎. 𝟏
𝟖𝟑𝟏𝟒 × 𝟑𝟎𝟖 × 𝟎. 𝟑×𝟏𝟎'𝟑
70

70

35
 11/03/2024

𝒎𝒐𝒍
𝑵𝑨 = 𝟏. 𝟔𝟔×𝟏𝟎'𝟑
𝒎𝟐 . 𝒔

𝑹𝒂𝒕𝒆 𝒐𝒇 𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏 = 𝑵𝑨 ×𝑨𝒓𝒆𝒂

𝒎𝒐𝒍 𝟑𝟔𝟎𝟎 𝒔 𝟒𝟔𝒌𝒈

𝑹𝒂𝒕𝒆 𝒐𝒇 𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏 = 𝟏. 𝟔𝟔×𝟏𝟎!𝟑 𝟐 ×𝟏𝟎𝟎×𝟏𝟎!𝟒 𝒎𝟐 × ×
𝒎 .𝒔 𝟏𝒉 𝒎𝒐𝒍

𝒌𝒈
𝑹𝒂𝒕𝒆 𝒐𝒇 𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏 = 𝟐. 𝟕𝟒𝟗×𝟏𝟎!𝟑
𝒉

71

71

(ii) Diffusion through a stagnant film

𝑫𝑨𝑩 𝑷𝒕 𝟏 − 𝒚𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝑹𝑻𝒁 𝟏 − 𝒚𝑨𝟏
𝟎. 𝟏𝟖×𝟏𝟎'𝟒 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓 𝟏 − 𝟎. 𝟏
𝑵𝑨 = 𝒍𝒏
𝟖𝟑𝟏𝟒 × 𝟑𝟎𝟖 × 𝟎. 𝟑×𝟏𝟎'𝟑 𝟏 − 𝟎. 𝟖
𝒎𝒐𝒍
𝑵𝑨 = 𝟑. 𝟓𝟕𝟎𝟔×𝟏𝟎'𝟑 𝟐
𝒎 .𝒔
𝑹𝒂𝒕𝒆 𝒐𝒇 𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏 = 𝑵𝑨 ×𝑨𝒓𝒆𝒂
𝒎𝒐𝒍 𝟑𝟔𝟎𝟎 𝒔 𝟒𝟔𝒌𝒈
𝑹𝒂𝒕𝒆 𝒐𝒇 𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏 = 𝟑. 𝟓𝟕𝟎𝟔×𝟏𝟎!𝟑 𝟐
×𝟏𝟎𝟎×𝟏𝟎!𝟒 𝒎𝟐 × ×
𝒎 .𝒔 𝟏𝒉 𝒎𝒐𝒍
𝒌𝒈
𝑹𝒂𝒕𝒆 𝒐𝒇 𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏 = 𝟓. 𝟗𝟏𝟐𝟗×𝟏𝟎!𝟑
𝒉 72

72

36
 11/03/2024

Example 8
Hydrogen gas at 1 standard atm and 25ºC flows through a pipe made
of unvulcanised neoprene rubber with ID and OD of 25 and 50 mm
respectively. If the concentration of hydrogen at the inner surface of the
pipe is 𝟐. 𝟑𝟕×𝟏𝟎'𝟑 kmol hydrogen/m3 and the diffusivity of hydrogen gas
through the rubber is 𝟏. 𝟖×𝟏𝟎'𝟔 cm2/s, estimate the rate of loss of
hydrogen by diffusion through a pipe of 2 m length. The outside air may
be assumed to be free from hydrogen.

Solution 𝑫𝑨 𝑺𝑨 𝒑𝑨𝟏 − 𝒑𝑨𝟐

𝑽𝑨 =
𝒁

𝑫𝑨 = 𝟏. 𝟖×𝟏𝟎'𝟔 𝒄𝒎𝟐 = 𝟏. 𝟖×𝟏𝟎'𝟏𝟎 𝒎𝟐

𝟓𝟎 − 𝟐𝟓
𝒁= = 𝟏𝟐. 𝟓 𝒎𝒎
𝟐
73

73

𝑫𝑨 𝑪𝑨𝟏 − 𝑪𝑨𝟐
𝑽𝑨 =
𝒁
𝟏. 𝟖×𝟏𝟎'𝟏𝟎 𝟐. 𝟑𝟕×𝟏𝟎'𝟑 − 𝟎
𝑽𝑨 =
𝟏𝟐. 𝟓×𝟏𝟎'𝟑

𝑽𝑨 = 𝟎. 𝟑𝟒𝟏𝟑×𝟏𝟎'𝟏𝟎 𝒎𝒐𝒍/𝒎𝟐 . 𝒔

𝟐𝝅𝒍 𝑶𝑫 − 𝑰𝑫
𝑺𝒂𝒗 =
𝑶𝑫
𝟐𝒍𝒏 𝑰𝑫

𝟐𝝅×𝟐×𝟐𝟓×𝟏𝟎'𝟑
𝑺𝒂𝒗 = = 𝟎. 𝟐𝟐𝟔𝟔 𝒎𝟐
𝟓𝟎
𝟐𝒍𝒏
𝟐𝟓 74

74

37
 11/03/2024

𝑹𝒂𝒕𝒆 = 𝑽𝑨 ×𝑺𝒂𝒗

𝑹𝒂𝒕𝒆 = 𝟎. 𝟑𝟒𝟏𝟑×𝟏𝟎'𝟏𝟎 ×𝟎. 𝟐𝟐𝟔𝟔

𝑹𝒂𝒕𝒆 = 𝟕. 𝟕𝟑𝟒×𝟏𝟎'𝟏𝟐 𝒎𝒐𝒍/𝒔

75

75

Example
An ethanol (A)-water (B) solution in the form of a stagnant film 2 mm
thick at 293 K is in contact at one surface with an organic solvent in
which ethanol is soluble and water is insoluble. Hence NB = 0. At point 1
the concentration of ethanol is 16.8 wt % and the solution density is 𝒑𝟏
= 𝟗𝟕𝟐. 𝟖 𝒌𝒈/𝒎𝟑 . At point 2 the concentration of ethanol is 6.8 wt % and
the solution density is 𝒑𝟐 = 𝟗𝟖𝟖. 𝟏 𝒌𝒈/𝒎𝟑 . The diffusivity of ethanol is
𝟎. 𝟕𝟒×𝟏𝟎'𝟗 𝒎𝟐 /𝒔. Calculate the steady state flux NA.

1 A-B 2
A A A A A A A A A A A A A A A
𝒄𝑨𝟏 = 𝟏𝟔. 𝟖 𝒘𝒕% 𝒄𝑨𝟐 = 𝟔. 𝟖 𝒘𝒕%

𝝆𝟏 = 𝟗𝟕𝟐. 𝟖 𝒌𝒈/𝒎𝟑 𝝆𝟐 = 𝟗𝟖𝟖. 𝟏 𝒌𝒈/𝒎𝟑

Organic solvent

76

38
 11/03/2024

𝑴𝑨 = 𝟒𝟔. 𝟎𝟔 𝒌𝒈/𝒎𝒐𝒍 𝑴𝑩 = 𝟏𝟖. 𝟎𝟐 𝒌𝒈/𝒎𝒐𝒍

Using 100 kg of solution as basis for calculation then:
𝒏𝑨𝟐 𝟔. 𝟖⁄𝟒𝟔. 𝟎𝟓
𝒙𝑨𝟐 = = = 𝟎. 𝟎𝟐𝟕𝟕
𝒏𝑨𝟐 + 𝒏𝑩𝟐 𝟔. 𝟖⁄𝟒𝟔. 𝟎𝟓 + 𝟗𝟑. 𝟐⁄𝟏𝟖. 𝟎𝟐
𝒙𝑩𝟐 = 𝟏 − 𝒙𝑨𝟐 = 𝟎. 𝟗𝟕𝟐𝟑
𝒏𝑨𝟏 𝟏𝟔. 𝟖⁄𝟒𝟔. 𝟎𝟓
𝒙𝑨𝟏 = = = 𝟎. 𝟎𝟕𝟕𝟑
𝒏𝑨𝟏 + 𝒏𝑩𝟏 𝟏𝟔. 𝟖⁄𝟒𝟔. 𝟎𝟓 + 𝟖𝟑. 𝟐⁄𝟏𝟖. 𝟎𝟐
𝒙𝑩𝟏 = 𝟏 − 𝒙𝑨𝟏 = 𝟎. 𝟗𝟐𝟔𝟖

77

To calculate the molecular weights M1 at point 1 and M2 at point 2:

𝑻𝒐𝒕𝒂𝒍 𝒎𝒂𝒔𝒔
𝑴𝟏 =
𝒏𝑨𝟏 + 𝒏𝑩𝟏
𝟏𝟎𝟎 𝟏𝟎𝟎
𝑴𝟏 = = = 𝟐𝟎. 𝟎𝟕 𝒌𝒈/𝒎𝒐𝒍
𝟏𝟔. 𝟖⁄𝟒𝟔. 𝟎𝟓 + 𝟖𝟑. 𝟐⁄𝟏𝟖. 𝟎𝟐 𝟎. 𝟑𝟔𝟓 + 𝟒. 𝟔𝟏𝟕
𝑻𝒐𝒕𝒂𝒍 𝒎𝒂𝒔𝒔
𝑴𝟐 =
𝒏𝑨𝟐 + 𝒏𝑩𝟐
𝟏𝟎𝟎 𝟏𝟎𝟎
𝑴𝟐 = = = 𝟏𝟖. 𝟕𝟓 𝒌𝒈/𝒎𝒐𝒍
𝟔. 𝟖⁄𝟒𝟔. 𝟎𝟓 + 𝟗𝟑. 𝟐⁄𝟏𝟖. 𝟎𝟐 𝟎. 𝟏𝟒𝟕𝟕 + 𝟓. 𝟏𝟕

78

39
 11/03/2024

𝝆𝟏 𝝆𝟐 𝟗𝟕𝟐. 𝟖 𝟗𝟖𝟖. 𝟏
+
𝑴𝟏 𝑴𝟐 𝟐𝟎. 𝟎𝟕 + 𝟏𝟖. 𝟕𝟓
𝒄𝒂𝒗 = = = 𝟓𝟎. 𝟔 𝒎𝒐𝒍/𝒎𝟑
𝟐 𝟐
𝒙𝑩𝟏 + 𝒙𝑩𝟐 𝟎. 𝟗𝟐𝟔𝟖 + 𝟎. 𝟗𝟕𝟐𝟑
𝒙𝑩𝑴 = = = 𝟎. 𝟗𝟒𝟗
𝟐 𝟐
𝑫𝑨𝑩 𝒄𝒂𝒗 𝒙𝑨𝟏 − 𝒙𝑨𝟐 𝟎. 𝟕𝟒×𝟏𝟎'𝟗 𝟓𝟎. 𝟔 𝟎. 𝟎𝟕𝟑𝟐 − 𝟎. 𝟎𝟐𝟕𝟕
𝑵𝑨 = =
𝒛𝟐 − 𝒛𝟏 𝒙𝑩𝑴 𝟐⁄𝟏𝟎𝟎𝟎 𝟎. 𝟗𝟒𝟗
𝒎𝒐𝒍
𝑵𝑨 = 𝟖. 𝟗𝟗×𝟏𝟎'𝟕
𝒔. 𝒎𝟐

79

Example 10
Carbon dioxide and oxygen experience equimolal counter diffusion in a
circular tube whose length and diameter are 1 m and 50 mm
respectively. The system is at a total pressure of 10 atm. and a
temperature of 25ºC. The ends of the tube are connected to large
chambers in which the species concentrations are maintained at fixed
values. The partial pressure of CO2 at one end is 190 mm Hg while at
the other end is 95 mm Hg.
(i) Estimate the rate of mass transfer.
(ii) Find the partial pressure of CO2 at 0.75 m from the end where the
partial pressure is 190 mm Hg.
Diffusivity under given condition is 𝟐. 𝟏×𝟏𝟎'𝟓 m2/s.

80

80

40
 11/03/2024

Solution 𝑫𝑨𝑩 𝒑𝑨𝟏 − 𝒑𝑨𝟐

𝑵𝑨 =
𝒁𝑹𝑻
𝒎𝟑
𝑷𝟎 𝑽𝟎 𝟕𝟔𝟎𝒎𝒎𝑯𝒈×𝟐𝟐. 𝟒𝟏𝟒 𝒎𝒐𝒍 𝒎𝒎𝑯𝒈. 𝒎𝟑
𝑹= = = 𝟔𝟐. 𝟒
𝑻𝟎 𝟐𝟕𝟑 𝑲 𝒎𝒐𝒍. 𝑲

𝟐. 𝟏×𝟏𝟎'𝟓 𝟏𝟗𝟎 − 𝟗𝟓 𝒎𝒐𝒍

𝑵𝑨 = = 𝟏. 𝟎𝟕𝟑×𝟏𝟎'𝟕 𝟐
𝟏×𝟔𝟐. 𝟒×𝟐𝟗𝟖 𝒎 .𝒔
𝟐
'𝟕 𝟐 '𝟕
𝟓𝟎×𝟏𝟎'𝟑
𝑹𝒂𝒕𝒆 = 𝟏. 𝟎𝟕𝟑×𝟏𝟎 ×𝝅𝒓 = 𝟏. 𝟎𝟕𝟑×𝟏𝟎 ×𝝅
𝟐

𝑹𝒂𝒕𝒆 = 𝟐. 𝟏𝟎𝟕×𝟏𝟎'𝟏𝟎 𝒎𝒐𝒍/𝒔

81

81

(ii) Find the partial pressure of CO2 at 0.75 m from the end where the
partial pressure is 190 mm Hg.
𝒚𝑨 − 𝒚𝑨𝟏 𝒁 − 𝒁𝟏
=
𝒚𝑨𝟐 − 𝒚𝑨𝟏 𝒁𝟐 − 𝒁𝟏
𝒑𝑨
𝒚=
𝑷𝒕
𝒑𝑨 − 𝒑𝑨𝟏 𝒁 − 𝒁𝟏
=
𝒑𝑨𝟐 − 𝒑𝑨𝟏 𝒁𝟐 − 𝒁𝟏
𝒑𝑨 − 𝟏𝟗𝟎 𝟎. 𝟕𝟓 − 𝟎
=
𝟗𝟓 − 𝟏𝟗𝟎 𝟏−𝟎

𝒑𝑨 = 𝟏𝟏𝟖. 𝟕𝟓 𝒎𝒎𝑯𝒈
82

82

41
 11/03/2024

Example 11
Ammonia is diffusing through an inert air film 2 mm thick at a
temperature of 20ºC and a pressure of 1 atm. The concentration of
ammonia is 10% by volume on one side of the film and zero on the other
side. Determine the mass flux. Estimate the effect on the rate of diffusion
if the pressure is increased to 10 atm. The diffusivity of NH3 in air at 20°C
and 1 atm. is 0.185 cm2/s.

Solution
Assuming air to be stagnant and non-diffusing,
𝑫𝑨𝑩 𝑷𝒕 𝟏 − 𝒚𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝑹𝑻𝒁 𝟏 − 𝒚𝑨𝟏

83

83

𝟎. 𝟏𝟖𝟓×𝟏𝟎'𝟒 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓 𝟏−𝟎

𝑵𝑨 = 𝒍𝒏
𝟖𝟑𝟏𝟒 × 𝟐𝟗𝟑 × 𝟐×𝟏𝟎'𝟑 𝟏 − 𝟎. 𝟏

𝒎𝒐𝒍
𝑵𝑨 = 𝟒. 𝟎𝟓×𝟏𝟎'𝟓
𝒎𝟐 . 𝒔

𝑴𝒂𝒔𝒔 𝒇𝒍𝒖𝒙 = 𝑵𝑨 ×𝑴𝒘

𝒌𝒈
𝑴𝒂𝒔𝒔 𝒇𝒍𝒖𝒙 = 𝟒. 𝟎𝟓×𝟏𝟎'𝟓 ×𝟏𝟕 = 𝟔. 𝟖𝟗×𝟏𝟎'𝟒
𝒎𝟐 . 𝒔
When pressure is increased to 10 atm, For gases,
𝟏
𝑫𝑨𝑩 ∝
𝑷𝒕 84

84

42
 11/03/2024

𝑫𝑨𝑩𝟏 𝑷𝒕𝟐
=
𝑫𝑨𝑩𝟐 𝑷𝒕𝟏

𝟎. 𝟏𝟖𝟓 𝟏𝟎
=
𝑫𝑨𝑩𝟐 𝟏
𝟐
𝑫𝑨𝑩𝟐 = 𝟎. 𝟎𝟏𝟖𝟓 𝒄𝒎 b𝒔

𝑫𝑨𝑩 𝑷𝒕 𝟏 − 𝒚𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝑹𝑻𝒁 𝟏 − 𝒚𝑨𝟏

𝟎. 𝟎𝟏𝟖𝟓×𝟏𝟎'𝟒 ×𝟏𝟎×𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓 𝟏−𝟎

𝑵𝑨 = 𝒍𝒏
𝟖𝟑𝟏𝟒 × 𝟐𝟗𝟑 × 𝟐×𝟏𝟎'𝟑 𝟏 − 𝟎. 𝟏
85

85

𝒎𝒐𝒍
𝑵𝑨 = 𝟒. 𝟎𝟓×𝟏𝟎'𝟓
𝒎𝟐 . 𝒔

So, rate of diffusion remains same on increasing the pressure.

86

86

43
 11/03/2024

Example 12
Alcohol vapour is being absorbed from a mixture of alcohol vapour and
water vapour by means of a nonvolatile solvent in which alcohol is soluble
but water is not. The temperature is 97°C and the total pressure is 760 mm
Hg. The alcohol vapour can be considered to be diffusing through a film of
alcohol–water–vapour mixture 0.1 mm thick. The mole % of alcohol in the
vapour at the outside of the film is 80%, and that on the inside, next to the
solvent is 10%. The diffusivity of alcohol–water vapour mixtures at 25°C
and 1 atm. Is 0.15 cm2/s. Calculate the rate of diffusion of alcohol vapour
in kg per hour if the area of the film is 10 m2.

87

87

Solution
For gases, 𝑫𝑨𝑩 ∝ 𝑻𝟑⁄𝟐

𝟑⁄𝟐
𝑫𝑨𝑩𝟏 𝑻𝟏
=
𝑫𝑨𝑩𝟐 𝑻𝟐

𝟑⁄𝟐
𝟎. 𝟏𝟓×𝟏𝟎'𝟒 𝟐𝟗𝟖
=
𝑫𝑨𝑩𝟐 𝟑𝟕𝟎

𝟐
𝑫𝑨𝑩𝟐@𝟗𝟕°𝑪 = 𝟐. 𝟎𝟕𝟓×𝟏𝟎'𝟓 𝒎 b𝒔

88

88

44
 11/03/2024

Water is insoluble in solvent and thus non-diffusing:

𝑫𝑨𝑩 𝑷𝒕 𝟏 − 𝒚𝑨𝟐
𝑵𝑨 = 𝒍𝒏
𝑹𝑻𝒁 𝟏 − 𝒚𝑨𝟏

𝟐. 𝟎𝟕𝟓×𝟏𝟎'𝟓 ×𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓 𝟏 − 𝟎. 𝟏

𝑵𝑨 = 𝒍𝒏
𝟖𝟑𝟏𝟒 × 𝟑𝟕𝟎 × 𝟎. 𝟏×𝟏𝟎'𝟑 𝟏 − 𝟎. 𝟖

𝒎𝒐𝒍
𝑵𝑨 = 𝟏. 𝟎𝟐𝟕𝟖×𝟏𝟎'𝟐
𝒎𝟐 . 𝒔

𝑹𝒂𝒕𝒆 = 𝟏. 𝟎𝟐𝟕𝟖×𝟏𝟎'𝟐 ×𝟏𝟎×𝟑𝟔𝟎𝟎×𝟒𝟔 = 𝟏. 𝟕𝟎×𝟏𝟎'𝟒 𝒌𝒈/𝒉

89

89

Example 13
In an experimental determination of diffusivity of toluene in air, Stefan’s
method is being used. A vertical glass tube 3 mm in diameter is filled
with liquid toluene to a depth of 20 mm from the top open end. After 275
hrs at 39.4ºC and a total pressure of 1 atm., the level has dropped to 80
mm from the top. Neglecting counter diffusion of air to replace the
liquid, estimate the diffusivity.

90

90

45
 11/03/2024

91

91

Solution
𝝆𝑻𝒐𝒍 = 𝟖𝟓𝟎 𝒌𝒈/𝒎𝟑 R = 8314 Nm/kmol. K
𝑷 𝑨 = 𝟕. 𝟔𝟒 𝒌𝑵/𝒎𝟐 𝑷 𝒕 = 𝟏 𝒂𝒕𝒎
𝑻 = 𝟑𝟏𝟐. 𝟒 𝑲 𝒕 = 𝟐𝟕𝟓 𝒉
𝒁 𝒕𝟎 = 𝟐𝟎×𝟏𝟎'𝟑 𝒎 𝒁 𝒕𝒕 = 𝟖𝟎×𝟏𝟎'𝟑 𝒎

Air is assumed to be stagnant or non-diffusing:

𝝆𝑨,𝑳 𝟖𝟓𝟎
𝑪𝑨,𝑳 = = = 𝟗. 𝟐𝟒 𝒎𝒐𝒍/𝒎𝟑
𝑴𝑳 𝟗𝟐
𝑷𝒕 𝟏. 𝟎𝟏𝟑×𝟏𝟎𝟓
𝑪𝑨 = = = 𝟎. 𝟎𝟑𝟗 𝒎𝒐𝒍/𝒎𝟑
𝑹𝑻 𝟖𝟑𝟏𝟒×𝟑𝟏𝟐. 𝟒
92

92

46
 11/03/2024

𝑷𝑨 𝟕. 𝟔𝟒
𝒙𝑨𝟏 = = = 𝟎. 𝟎𝟕𝟓𝟒
𝑷𝒕 𝟏𝟎𝟏. 𝟑

𝒙𝑩𝟏 = 𝟏 − 𝒙𝑨𝟏 = 𝟏 − 𝟎. 𝟎𝟕𝟓𝟒 = 𝟎. 𝟗𝟐𝟒𝟔

𝒙𝑨𝟐 = 𝟎 𝒙𝑩𝟐 = 𝟏
𝒙𝑩𝟐 − 𝒙𝑩𝟏 𝟏 − 𝟎. 𝟗𝟐𝟒𝟔
𝒙𝑩,𝑴 = 𝒙𝑩𝟐 = = 𝟎. 𝟗𝟔𝟏𝟖
𝒍𝒏 𝒙 𝟏
𝒍𝒏 𝟎. 𝟗𝟐𝟒𝟔
𝑩𝟏

𝒕 𝒙𝑩,𝑴 𝑪𝑨,𝑳 𝒁𝒕 + 𝒁𝒕𝟎

=
𝒁𝒕 − 𝒁𝒕𝟎 𝟐×𝑪×𝑫𝑨𝑩 𝒙𝑨𝟏 − 𝒙𝑨𝟐

93

93

𝒙𝑩,𝑴 𝑪𝑨,𝑳 𝒁𝟐𝒕 − 𝒁𝟐𝒕𝟎

𝑫𝑨𝑩 =
𝟐×𝑪 𝒙𝑨𝟏 − 𝒙𝑨𝟐 ×𝒕

𝟐 𝟐
𝟎. 𝟗𝟔𝟏𝟖×𝟗. 𝟐𝟒 𝟖𝟎×𝟏𝟎'𝟑 − 𝟐𝟎×𝟏𝟎'𝟑
𝑫𝑨𝑩 =
𝟐×𝟎. 𝟎𝟑𝟗 𝟎. 𝟎𝟕𝟓𝟒 − 𝟎 ×𝟐𝟕𝟓×𝟑𝟔𝟎𝟎

𝟐
𝑫𝑨𝑩 = 𝟎. 𝟗𝟏𝟔×𝟏𝟎'𝟓 𝒎 b𝒔

94

94

47