Analogy of Mass, Heat and Momentum

Transport

General molecular transport equations

𝑑Γ
𝜓𝑧 = −𝛿
𝑑𝑧
Momentum Heat Mass
𝜇 𝑑 (𝜌𝑣𝑥 ) 𝑞𝑧 𝑑 (𝜌𝐶𝑃 𝑇) ⋆
𝑑 (𝑐𝐴 )
𝜏𝑧𝑥 = − ( ) = −𝛼 𝐽𝐴𝑧 = −𝐷𝐴𝐵
𝜌 𝑑𝑧 𝐴 𝑑𝑧 𝑑𝑧

Turbulent diffusion equation

Momentum Heat Mass
𝜇 𝑑 (𝜌𝑣𝑥 ) 𝑞𝑧 ⋆
𝐽𝐴𝑧
𝜏𝑧𝑥 = − ( + 𝜀𝑡 ) 𝐴 𝑑 (𝑐𝐴 )
𝜌 𝑑𝑧 = −(𝐷𝐴𝐵 + 𝜀𝑀 )
𝑑 (𝜌𝐶𝑃 𝑇)
= −(𝛼 + 𝛼𝑡 ) 𝑑𝑧
𝑑𝑧
Diffusion
Diffusion results from random motions of two types: the random motion of
molecules in a fluid, and the random eddies which arise in turbulent flow.
Diffusion from the random molecular motion is termed molecular diffusion;
diffusion which results from turbulent eddies is called turbulent diffusion or
eddy diffusion.

Why diffusion occurs?

Initially, there are solute molecules (A) on the left side of a barrier and
none on the right. The barrier is removed, and the solute (A) diffuses into B
to fill the whole container.

Diffusion of molecules is due to concentration gradient.

Momentum 𝜇 𝑚2
( ) ( )
diffusivity 𝜌 𝑠

𝑚2
Thermal diffusivity 𝛼 ( )
𝑠

𝑚2
Molecular diffusivity 𝐷𝐴𝐵 ( )
𝑠
  Molecular diffusivity depends on pressure, temperature, and
composition of the system.
 Diffusivities of gases at low density are almost composition
independent, increase with the temperature and vary inversely with
pressure (Table 6.2-1 CJG).
 Liquid and solid diffusivities are strongly concentration dependent
and increase with temperature.

General range of diffusivities:

 Gases: 5 × 10 –6 – 1 × 10-5 m2 / s
 Liquids: 10 –6 – 10-9 m2 / s
 Solids: 5 × 10 –14 – 1 × 10-10 m2 / s

In the absence of experimental data, semi-theoretical expressions have been

developed which give approximate values of molecular diffusivities.

𝑚2
Turbulent (eddy) momentum diffusivity 𝜀𝑡 ( )
𝑠

𝑚2
Turbulent (eddy) thermal diffusivity 𝛼𝑡 ( )
𝑠

𝑚2
Turbulent (eddy) mas diffusivity 𝜀𝑀 ( )
𝑠
Fick’s Law for Molecular Diffusion
⋆
𝑑 (𝑥𝐴 )
𝐽𝐴𝑧 = −𝑐𝐷𝐴𝐵
𝑑𝑧
where c is the total concentration of A and B in (kg mol A + B)/m3, and 𝑥𝐴
is the mole fraction of A in the mixture A and B.

For constant concentration (c),

𝑐𝐴 = 𝑐𝑥𝐴
𝑑𝑐𝐴 = 𝑑 (𝑐𝑥𝐴 ) = 𝑐𝑑 (𝑥𝐴 )

⋆
𝑑(𝑐𝐴 )
𝐽𝐴𝑧 = −𝐷𝐴𝐵
𝑑𝑧

For constant molar flux, the above equation can be integrated as follows to
give,

𝑧2 𝑐𝐴2
⋆
𝐽𝐴𝑧 ∫ 𝑑𝑧 = −𝐷𝐴𝐵 ∫ 𝑑(𝑐𝐴 )
𝑧1 𝑐𝐴1

⋆
𝐷𝐴𝐵 (𝑐𝐴1 − 𝑐𝐴2 )
𝐽𝐴𝑧 =−
(𝑧1 − 𝑧2 )

Since the concentration is related to partial pressure,

𝑝𝐴
𝑐𝐴 =
𝑅𝑇

⋆
𝐷𝐴𝐵 (𝑝𝐴1 − 𝑝𝐴2 )
𝐽𝐴𝑧 =−
𝑅𝑇 (𝑧1 − 𝑧2 )

⋆
𝐷𝐴𝐵 1
𝐽𝐴𝑧 = (𝑝 − 𝑝𝐴2 )
(𝑧2 − 𝑧1 ) 𝑅𝑇 𝐴1
Gas constants: R_ 8314 (m3.Pa)/(kg mol . K)

Example 6.1-1: Molecular diffusion of Helium in Nitrogen

Helium-N2 @ 298 K
T 298 K
P 1.013E+05 Pa
D_AB1 6.870E-05 m2/s
p_A1 6.080E+04 Pa
p_A2 2.027E+04 Pa
dZ 0.2 m
2
J_AZ1 5.6192E-06 (kg mol A)/(s.m )

Diffusivity Helium-N2 @ 398 K

T_1 298 K
D_AB1 6.87E-05 Pa
T_2 398 K
D_AB2 1.14E-04 Pa

Helium-N2 @ 398 K
T 398 K
P 1.013E+05 Pa
D_AB2 1.140E-04 m2/s
p_A1 6.080E+04 Pa
p_A2 2.027E+04 Pa
dZ 0.2 m
J_AZ2 6.9812E-06 (kg mol A)/(s.m2)
Change 24.2 %
Molecular Diffusion in Gases
Equi-molar Counter Diffusion in Gasses

Consider diffusion that occurs in a tube connecting two tanks containing a

binary gas mixture of species A and B. If both tanks as well as the connecting
tube are at a uniform pressure and temperature, the total molar concentration
would be uniform throughout the tanks and the connecting tube. If 𝑥𝐴1 , the
mole fraction of A in tank 1, is larger than 𝑥𝐴2 , the mole fraction of A in
tank 2, A would diffuse from tank 1 to tank 2 through the connecting tube,
while B would diffuse from tank 2 to tank 1 through the same connecting
tube.
Because the temperature and pressure are uniform, the molar flux of
A from tank 1 to tank 2 through the connecting tube must be the
same as the molar flux of B from tank 2 to tank 1.
⋆ ⋆
𝐽𝐴𝑧 = −𝐽𝐵𝑧

𝑑 (𝑐𝐴 ) 𝑑(𝑐𝐵 )
[−𝐷𝐴𝐵 ] = − [−𝐷𝐵𝐴 ]
𝑑𝑧 𝑑𝑧

Since, 𝑃 = 𝑝𝐴 + 𝑝𝐵 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, therefore,

𝑐 = 𝑐𝐴 + 𝑐𝐵 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡.
Differentiating
0 = 𝑑𝑐𝐴 + 𝑑𝑐𝐵
Substituting 𝑑𝑐𝐵 = −𝑑𝑐𝐴 gives,
𝑑(𝑐𝐴 ) 𝑑 (𝑐𝐵 ) 𝑑 (𝑐𝐴 ) 𝑑 (𝑐𝐴 )
[−𝐷𝐴𝐵 ] = − [−𝐷𝐵𝐴 ] = − [−𝐷𝐵𝐴 (− )] = [−𝐷𝐵𝐴 ]
𝑑𝑧 𝑑𝑧 𝑑𝑧 𝑑𝑧

𝑑 (𝑐𝐴 ) 𝑑 (𝑐𝐴 )
[−𝐷𝐴𝐵 ] = [−𝐷𝐵𝐴 ]
𝑑𝑧 𝑑𝑧

𝐷𝐴𝐵 = 𝐷𝐵𝐴

Conclusion
For a binary gas mixture of A and B. the diffusion coefficient
for A diffusing in B is same as gas B diffusing in A.
Molecular diffusivity is independent of concentration.
Example 6.2-1: Equimolar Counter Diffusion

T 298 K
P 1.01E+05 Pa
D_AB1 2.30E-05 m2/s
p_A1 1.01E+04 Pa
p_A2 5.07E+03 Pa
dZ 0.1 m
J_AZ 4.6973E-07 (kg mol A)/(s.m2)

T 298 K
P 1.01E+05 Pa
D_AB1 2.30E-05 m2/s
p_B1 9.12E+04 Pa
p_B2 9.63E+04 Pa
dZ 0.1 m
J_BZ -4.697E-07 (kg mol A)/(s.m2)
Diffusion of Gases A and B with Convective Flow
Diffusion velocity (m/s) of A = 𝑣𝐴𝑑

Therefore, molar diffusion flux,

⋆
𝑘𝑔 𝑚𝑜𝑙 𝐴 𝑘𝑔 𝑚𝑜𝑙 𝐴 𝑚
𝐽𝐴𝑧 = 𝑐𝐴 𝑣𝐴𝑑
𝑠 ∙ 𝑚2 𝑚3 𝑠
The velocity of A relative to the stationary point is the sum of the diffusion velocity
(𝑣𝐴𝑑 ) and the average velocity (𝑣𝑀 , molar average velocity of the whole fluid relative
to a stationary point). Mathematically,

𝑣𝐴 = 𝑣𝐴𝑑 + 𝑣𝑀

𝑐𝐴 𝑣𝐴 = 𝑐𝐴 𝑣𝐴𝑑 + 𝑐𝐴 𝑣𝑀

Total flux of A relative Diffusion flux relative Convective flux of A

to stationary point = to moving fluid
⋆ )
+ relative to stationary
𝑐𝐴 𝑣𝐴 (= 𝑁𝐴 ) 𝑐𝐴 𝑣𝐴𝑑 (=, 𝐽𝐴𝑧 point 𝑐𝐴 𝑣𝑀

Total convective flux of the whole stream relative to the stationary point:

𝑁𝐴 + 𝑁𝐵
𝑐𝑣𝑀 = 𝑁 = 𝑁𝐴 + 𝑁𝐵 ; 𝑣𝑀 =
𝑐

Convective flux of A,
Total flux of = ⋆
Diffusion flux, 𝐽𝐴𝑧 + 𝑐𝐴 (
𝑁𝐴 + 𝑁𝐵
)
A, 𝑁𝐴 𝑐

Therefore,

𝑑(𝑥𝐴 ) 𝑐𝐴
𝑁𝐴 = −𝑐𝐷𝐴𝐵 + (𝑁𝐴 + 𝑁𝐵 )
𝑑𝑧 𝑐
𝑑(𝑥𝐵 ) 𝑐𝐵
𝑁𝐵 = −𝑐𝐷𝐵𝐴 + (𝑁𝐴 + 𝑁𝐵 )
𝑑𝑧 𝑐
Special Case for A Diffusing through Stagnant Film of B

Example 1: The benzene vapor (A) diffuses through the air (B) in the tube. The air is
insoluble in benzene liquid, there is no movement in air (𝑁𝐵 = 0).

Example 2: The ammonia vapor (A) diffuses through the air (B) in the tube and gets
absorbed in water. The air is slightly soluble in water, there is no
movement in air (𝑁𝐵 = 0).

Therefore,
𝑑 (𝑥𝐴 ) 𝑐𝐴
𝑁𝐴 = −𝑐𝐷𝐴𝐵 + (𝑁𝐴 + 0)
𝑑𝑧 𝑐
Since,
𝑃 𝑐𝐴 𝑝𝐴
𝑐= ; 𝑝𝐴 = 𝑥𝐴 𝑃; =
𝑅𝑇 𝑐 𝑃

Therefore, for constant pressure

𝐷𝐴𝐵 𝑑(𝑝𝐴 ) 𝑝𝐴
𝑁𝐴 = − + 𝑁𝐴
𝑅𝑇 𝑑𝑧 𝑃
𝑝𝐴 𝐷𝐴𝐵 𝑑 (𝑝𝐴 )
𝑁𝐴 (1 − )=−
𝑃 𝑅𝑇 𝑑𝑧
 𝑷 𝟏 𝒅(𝒑𝑨 )
𝑵𝑨 = −𝑫𝑨𝑩
𝑹𝑻 (𝑷 − 𝒑𝑨 ) 𝒅𝒛

𝑍2
𝑃 𝑝𝐴2 𝑑𝑝𝐴
𝑁𝐴 ∫ 𝑑𝑧 = −𝐷𝐴𝐵 ∫
𝑍1 𝑅𝑇 𝑝𝐴1 (𝑃 − 𝑝𝐴 )

𝐷𝐴𝐵 𝑃 𝑃 − 𝑝𝐴2
𝑁𝐴 = ln
(𝑧2 − 𝑧1 ) 𝑅𝑇 𝑃 − 𝑝𝐴1

Since, the total pressure is the sum of partial pressures, i.e., 𝑃 = 𝑝𝐴1 + 𝑝𝐵1 = 𝑝𝐴2 +
𝑝𝐵2
Therefore,

𝐷𝐴𝐵 𝑃 𝑝𝐵2
𝑁𝐴 = 𝑙𝑛
(𝑧2 − 𝑧1 ) 𝑅𝑇 𝑝𝐵1

But,

𝑝𝐵2 − 𝑝𝐵1 𝑝𝐴1 − 𝑝𝐴2

𝑝𝐵𝑀 = 𝑝 = 𝑝
𝑙𝑛 𝐵2 𝑙𝑛 𝐵2
𝑝𝐵1 𝑝𝐵1

𝑝𝐵2 𝑝𝐴1 − 𝑝𝐴2

𝑙𝑛 =
𝑝𝐵1 𝑝𝐵𝑀

Therefore,

𝑫𝑨𝑩 𝑷 𝒑𝑨𝟏 − 𝒑𝑨𝟐

𝑵𝑨 =
(𝒛𝟐 − 𝒛𝟏 ) 𝑹𝑻 𝒑𝑩𝑴
 𝑫𝑨𝑩 𝟏 𝑷
𝑵𝑨 = (𝒑𝑨𝟏 − 𝒑𝑨𝟐 )
(𝒛𝟐 − 𝒛𝟏 ) 𝑹𝑻 𝒑𝑩𝑴
𝑫𝑨𝑩 𝟏
𝑱⋆𝑨𝒛 = (𝒑𝑨𝟏 − 𝒑𝑨𝟐 )
(𝒛𝟐 − 𝒛𝟏 ) 𝑹𝑻
EXAMPLE 6.2-2: Diffusion of Water Through Stagnant,
Non-diffusing Air

Water in the bottom of a narrow metal tube is held at a constant

temperature of 293 K. The total pressure of air (assumed dry) is 1.01325 ×
105 Pa (1.0 atm) and the temperature is 293 K (20°C). Water evaporates and
diffuses through the air in the tube and the diffusion path (𝑧2 − 𝑧1 ) is
0.1524 m long. The diagram is similar to Fig. 6.2-2a. Calculate the rate of
evaporation at steady state. The diffusivity of water vapor at 293 K and 1
atm pressure is 0.250×10-4 m2/s. Assume that the system is isothermal.
Solution:
𝑝𝐴1 = 2.341 × 103 Pa (Vapor pressure of water at 20°C from Appendix A.2)
𝑝𝐴2 = 0 (Assuming dry air, i.e. no water vapor)
𝑝𝐵1 = P – pAl = 1.01325 × 105 – 2.341 × 103 = 98984
𝑝𝐵2 = P – pA2 = 1.01325 × 105 – 0 = 1.01325 × 105 Pa
𝑝𝐵2 − 𝑝𝐵1 𝑝𝐴1 − 𝑝𝐴2
𝑝𝐵𝑀 = 𝑝 = 𝑝 = 100149.4 𝑃𝑎
𝑙𝑛 𝐵2 𝑙𝑛 𝐵2
𝑝𝐵1 𝑝𝐵1
When,
𝑝𝐵1 + 𝑝𝐵2
𝑝𝐵1 ≈ 𝑝𝐵2 ; 𝑝𝐵𝑀 ≅ = 100154.5 𝑃𝑎
2
𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2
𝑁𝐴 =
(𝑧2 − 𝑧1 ) 𝑅𝑇 𝑝𝐵𝑀
0.25 × 10−4 1.01325 × 105 (2.341 × 103 − 0) 𝑘𝑔 𝑚𝑜𝑙
= = 1.595 × 10−7 2
0.1524 8314 × 293 100149.4 𝑚 ∙𝑠
Question: Water at 20°C is flowing in a covered irrigation ditch below
ground. There is a vent line 30 mm inside diameter and 1.0 m long to the
outside atmosphere at 20°C. The percent relative humidity in Riyadh under
present weather conditions is about 10%. As a result, the partial pressure
of the water vapor in the outside air can be taken as 234 Pa. Determine the
molar flux of water vapor in (𝑘𝑔 𝑚𝑜𝑙⁄𝑚2 ∙ 𝑠)
(Data: Use the diffusivity data from Table 6.2-1. You may need to change its
value to the required temperature if needed. Vapor pressure of water vapor
at 20°C = 2340 Pa)

Solution:

𝑇 = 293 𝐾; 𝑃 = 1.01325 × 105 𝑃𝑎; 𝐷𝐴𝐵

= 2.6 × 10−5 𝑚2 ⁄𝑠 @298 𝐾;

𝐷𝐴𝐵2 𝑇2 1.75 −5
293 1.75
=( ) ; 𝐷𝐴𝐵2 = 2.6 × 10 ( ) = 𝟐. 𝟓𝟐 × 𝟏𝟎−𝟓 𝒎𝟐 ⁄𝒔
𝐷𝐴𝐵1 𝑇1 298

𝑝𝐴1 = 2340 Pa (Vapor pressure of water vapor at 20°C)

𝑝𝐴2 = 234 (10% Relative Humidity)
𝑝𝐵1 = P – 𝑝𝐴1 = 101.325 × 103 – 2.34 × 103 = 98,985 Pa
𝑝𝐵2 = P – 𝑝𝐴2 = 101325 – 234 = 101,091 Pa
𝑝𝐵2 − 𝑝𝐵1 𝑝𝐴1 − 𝑝𝐴2
𝑝𝐵𝑀 = 𝑝𝐵2 = 𝑝𝐵2 = 100,034 𝑃𝑎
𝑙𝑛 𝑙𝑛
𝑝𝐵1 𝑝𝐵1
𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2
𝑁𝐴 =
(𝑧2 − 𝑧1 ) 𝑅𝑇 𝑝𝐵𝑀
2.52 × 10−5 1.01325 × 105 (2340 − 234)
=
1.0 8314 × 293 100,034
𝒌𝒈 𝒎𝒐𝒍
= 𝟐. 𝟐𝟏 × 𝟏𝟎−𝟖
𝒎𝟐 ∙ 𝒔
Question 1 (33 pts): Water in the bottom of a narrow metal tube is held at a
temperature of 303 K. The total pressure of air (assumed dry) is 1.01325 x 105 Pa (1.0 atm)
and the temperature is 303 K. Water evaporates and diffuses through the air in the tube
and the diffusion path (z2 - z1) is 0.2 m long. The tube diameter is 10 mm. The diagram is
similar to Fig. 6.2-2a. The vapor pressure of water vapors at 303 K is 4242 Pa. The
experimental value of the diffusion coefficient at 298 K is 2.6×10-5 m2/s.

I. Determine the molecular diffusion coefficient at 303 K. 7

𝐷𝐴𝐵2 𝑇2 1.75 −5
303 1.75
=( ) ; 𝐷𝐴𝐵2 = 2.6 × 10 ( ) = 𝟐. 𝟔𝟖 × 𝟏𝟎−𝟓 𝒎𝟐 ⁄𝒔
𝐷𝐴𝐵1 𝑇1 298

II. Determine pBM in Pa. 5

𝑝𝐵2 − 𝑝𝐵1 𝑝𝐴1 − 𝑝𝐴2 4242 − 0
𝑝𝐵𝑀 = 𝑝𝐵2 = 𝑝𝐵2 = = 𝟗𝟗, 𝟏𝟖𝟗𝑷𝒂
𝑙𝑛 𝑙𝑛 101325 − 0
𝑝𝐵1 𝑝𝐵1 𝑙𝑛
101325 − 4242
III. Calculate the rate of evaporation (NA) at steady state in 𝑘𝑔 𝑚𝑜𝑙⁄𝑚2 ∙ 𝑠 and 13
𝑘𝑔⁄𝑚2 ∙ 𝑠
𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2
𝑁𝐴 =
(𝑧2 − 𝑧1 ) 𝑅𝑇 𝑝𝐵𝑀
2.68 × 10−5 1.01325 × 105 (4242 − 0) 𝒌𝒈 𝒎𝒐𝒍
= = 𝟐. 𝟑 × 𝟏𝟎−𝟕
0.2 8314 × 303 99,189 𝒎𝟐 ∙ 𝒔
𝒌𝒈
= 𝟒𝟏. 𝟒 × 𝟏𝟎−𝟕 𝟐
𝒎 ∙𝒔
IV. Calculate the steady state rate of evaporation (NA) if the air is humid (not dry) 8
and the percentage relative humidity, i.e. 100(𝑝𝐴 ⁄𝑝𝐴𝑜 ) = 30%, where 𝑝𝐴 is
the partial pressure of the water vapor in the air and 𝑝𝐴𝑜 is the vapor pressure.
30 𝑜
𝑝𝐴2 = 𝑝 = 0.3 × 4242 = 1273𝑃𝑎
100 𝐴
4242 − 1273
𝑝𝐵𝑀 = = 98,560 𝑃𝑎
101325 − 1273
𝑙𝑛
101325 − 4242
𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2
𝑁𝐴 =
(𝑧2 − 𝑧1 ) 𝑅𝑇 𝑝𝐵𝑀
2.68 × 10−5 1.01325 × 105 (4242 − 1273) 𝒌𝒈 𝒎𝒐𝒍
= = 𝟏. 𝟔𝟐 × 𝟏𝟎−𝟕
0.2 8314 × 303 98,560 𝒎𝟐 ∙ 𝒔
Note: There is almost 30% decrease in the flux due to a 30% decrease in
driving force since the change in the 𝑝𝐵𝑀 is negligible.
Interface Fall for A Diffusing through Stagnant Film of B
The initial and final heights are
𝑧0 , 𝑧𝐹 respectively.
If the level drops dz m in dt s, and
the total rate of diffusion due to
evaporation (in kg mol per s) will be

𝑁𝐴 = 𝑁𝐴 × 𝐴𝑟𝑒𝑎
𝑁𝐴 × 𝐴𝑟𝑒𝑎
𝜌𝐴 𝑑𝑧
= × 𝐴𝑟𝑒𝑎
𝑀𝐴 𝑑𝑡
𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2 𝜌𝐴 𝑑𝑧
=
𝑧 𝑅𝑇 𝑝𝐵𝑀 𝑀𝐴 𝑑𝑡
𝑃 𝑝𝐴1 − 𝑝𝐴2 𝑡𝐹 𝜌𝐴 𝑧𝐹
𝐷𝐴𝐵 ∫ 𝑑𝑡 = ∫ 𝑧𝑑𝑧
𝑅𝑇 𝑝𝐵𝑀 0 𝑀𝐴 𝑧0

𝜌𝐴 (𝑧𝐹2 −𝑧02 ) 𝑃 𝑝𝐴1 − 𝑝𝐴2 −𝟏

𝑡𝐹 = ( )
𝑀𝐴 2𝐷𝐴𝐵 𝑅𝑇 𝑝𝐵𝑀

The above equation can be used to experimentally determine the molecular diffusivity
𝐷𝐴𝐵 .

𝑃 𝑝𝐴1 − 𝑝𝐴2 𝑀𝐴
(𝑧𝐹2 −𝑧02 ) = ( ) ( ) (2𝐷𝐴𝐵 )𝑡𝐹
𝑅𝑇 𝑝𝐵𝑀 𝜌𝐴
Diffusion through a Varying Cross-Sectional Area
Case (A): Diffusion from a sphere:
Example:
 Evaporation of a drop of liquid
 Evaporation of a ball of
naphthalene
 Diffusion of nutrients from a
spherical micro-organism
Consider a sphere of A of radius 𝑟1 in an
infinite medium of gas B. Component A at partial pressure 𝑝𝐴1 at the surface is
diffusing in the surrounding stagnant medium (B), where 𝑝𝐴2 = 0 at large distance
away.
𝑘𝑔 𝑚𝑜𝑙 𝑘𝑔 𝑚𝑜𝑙
If the area changes, the flux (𝑁𝐴 ) will also change, but (𝑁𝐴 ) will remain
𝑚2 𝑠 𝑠
constant. For spherical geometry,

𝑁𝐴 𝑃 1 𝑑𝑝𝐴
𝑁𝐴 = == −𝐷𝐴𝐵
4𝜋𝑟 2 𝑅𝑇 (𝑃 − 𝑝𝐴 ) 𝑑𝑟

𝑁𝐴 𝑟2 𝑑𝑟 𝑃 𝑝𝐴2 1
∫ 2 = −𝐷𝐴𝐵 ∫ 𝑑𝑝
4𝜋 𝑟1 𝑟 𝑅𝑇 𝑝𝐴1 (𝑃 − 𝑝𝐴 ) 𝐴

𝑁𝐴 1 1 𝑃 𝑃 − 𝑝𝐴2
( − ) = 𝐷𝐴𝐵 ln
4𝜋 𝑟1 𝑟2 𝑅𝑇 𝑃 − 𝑝𝐴1

For 𝑟2 ≫ 𝑟1 , 1⁄𝑟2 ≅ 0, gives

𝑁𝐴 𝑃 𝑃 − 𝑝𝐴2
= 𝐷𝐴𝐵 ln
4𝜋𝑟1 𝑅𝑇 𝑃 − 𝑝𝐴1

𝑁𝐴 𝐷𝐴𝐵 𝑃 𝑃 − 𝑝𝐴2 𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2

𝑁𝐴 = = [ln ] = [ ]
4𝜋𝑟12 𝑟1 𝑅𝑇 𝑃 − 𝑝𝐴1 𝑟1 𝑅𝑇 𝑝𝐵𝑀
For 𝑝𝐴1 ≪ 𝑃 ⇒ 𝑝𝐵𝑀 ≅ 𝑃 . Therefore,
𝐷𝐴𝐵 1
𝑁𝐴 = (𝑝 − 𝑝𝐴2 )
𝑟1 𝑅𝑇 𝐴1
Since 𝑐 = 𝑃⁄𝑅𝑇 for liquids
𝐷𝐴𝐵
𝑁𝐴 = (𝑐 − 𝑐𝐴2 )
𝑟1 𝐴1
For a tube of constant cross-sectional area, the total time of evaporation for the change
in level from 𝑧0 to 𝑧𝐹 :

𝜌𝐴 (𝑧𝐹2 −𝑧02 ) 𝑃 𝑝𝐴1 − 𝑝𝐴2 −𝟏

𝑡𝐹 = ( )
𝑀𝐴 2𝐷𝐴𝐵 𝑅𝑇 𝑝𝐵𝑀
For a sphere, for the complete evaporation of initial radius 𝑟1 :

𝜌𝐴 (𝑟12 ) 𝑃 𝑝𝐴1 − 𝑝𝐴2 −𝟏

𝑡𝐹 = ( )
𝑀𝐴 2𝐷𝐴𝐵 𝑅𝑇 𝑝𝐵𝑀
Time to Completely Evaporate a Sphere
A drop of liquid toluene is kept at a uniform temperature of 25.9 °C and is suspended
in air by a fine wire. The initial radius 𝑟0 = 2𝑚𝑚. The vapor pressure of toluence at
25.9 °C is 𝑝𝐴1 = 3.84 𝑘𝑃𝑎 and the density of liquid toluene is 866 kg/m3. Calculate the
time in seconds for complete evaporation, i.e. 𝑟𝐹 = 0 𝑚𝑚.

𝜌𝐴 (𝑟02 − 𝑟𝐹2 ) 𝑃 𝑝𝐴1 − 𝑝𝐴2 −𝟏 𝜌𝐴 (𝑟02 − 𝑟𝐹2 ) 𝑅𝑇 𝑝𝐵𝑀

𝑡𝐹 = ( ) =
𝑀𝐴 2𝐷𝐴𝐵 𝑅𝑇 𝑝𝐵𝑀 𝑀𝐴 2𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2
 Question 2 (33 pts):
Water drop (spherical) is suspended in still air (assumed dry) by a fine wire
at 303K at 1.01325 x 105 Pa (1.0 atm). Its initial radius was r0 = 4 mm. The
vapor pressure of water at 303 K is 𝑝𝐴0 = 4242 𝑃𝑎 and the density of water
is 995.71 kg/m3. Note that
 Conditions in this problem are same as in Question 1
 𝐴𝑟𝑒𝑎, 𝐴 = 4𝜋𝑟 2 ; 𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉 = (4⁄3)𝜋𝑟 3 ; 𝑀𝑎𝑠𝑠 = 𝜌𝑉
 The time of evaporation can be computed using,
𝜌𝐴 (𝑟02 − 𝑟𝐹2 ) 𝑅𝑇 𝑝𝐵𝑀
𝑡𝐹 =
𝑀𝐴 2𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2
I. Calculate the time in seconds for its complete evaporation (rF = 0 mm). 12

𝜌𝐴 (𝑟02 − 𝑟𝐹2 ) 𝑅𝑇 𝑝𝐵𝑀 995.71 (0.0042 − 0) 8314 × 303 99,189

𝑡𝐹 = = = 𝟗𝟓𝟗𝟗 𝒔
𝑀𝐴 2𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2 18 2 ∙ 2.68 × 10−5 101325 4242 − 0

II. Calculate the time in second required for the evaporation of half of the total initial mass 10
of the water drop
𝑀𝑎𝑠𝑠F 𝑉𝑜𝑙𝑢𝑚𝑒F 𝑟F3
= = = 0.5; 𝑟F3 = 0.5𝑟i3 ; 𝑟𝐹 = 3.175 𝑚𝑚
𝑀𝑎𝑠𝑠i 𝑉𝑜𝑙𝑢𝑚𝑒i 𝑟i3
𝜌𝐴 (𝑟02 − 𝑟𝐹2 ) 𝑅𝑇 𝑝𝐵𝑀 995.71 (0.0042 − 0.0031752 ) 8314 × 303 99,189
𝑡𝐹 = =
𝑀𝐴 2𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2 18 2 ∙ 2.68 × 10−5 101325 4242 − 0
= 𝟑𝟓𝟓𝟏 𝒔

III. How much time in seconds will be required for its complete evaporation (rF = 0 mm) if 5
initial radius was r0 = 2 mm. (Detailed calculations not required).
Since 𝑡𝐹 ∝ 𝑟02 decreasing the initial radius by (1/2) will cause a (1/4) in the time of evaporation,
i.e. (9599/4) = 2400 s.

IV. Calculate the time in seconds for its complete evaporation when P = 0.1 atm = 1.01325 x 6
104 Pa
𝜌𝐴 (𝑟02 − 𝑟𝐹2 ) 𝑅𝑇 𝑝𝐵𝑀 995.71 (0.0042 − 0 ) 8314 × 303 𝟕, 𝟖𝟐𝟏
𝑡𝐹 = = = 𝟕𝟓𝟕𝒔
𝑀𝐴 2𝐷𝐴𝐵 𝑃 𝑝𝐴1 − 𝑝𝐴2 18 2 ∙ 26.8 × 10−5 10132.5 4242 − 0
Note: (𝐷𝐴𝐵 𝑃)is independent of pressure, but (𝑝𝐵𝑀 ) will change.
Case (B): Diffusion through a tapered conduit:
The radius at any location is related to length as
𝑟2 − 𝑟1
𝑟=( ) 𝑧 + 𝑟1
𝑧2 − 𝑧1
and area
𝑟2 − 𝑟1 2
2
𝐴 = 𝜋𝑟 = 𝜋 [( ) 𝑧 + 𝑟1 ]
𝑧2 − 𝑧1
Therefore,

𝑁𝐴 𝑃 1 𝑑𝑝𝐴
𝑁𝐴 = == −𝐷𝐴𝐵
𝜋𝑟 2 𝑅𝑇 (𝑃 − 𝑝𝐴 ) 𝑑𝑟

𝑁𝐴 𝑟2 𝑑𝑧 𝑃 𝑝𝐴2 1
𝑁𝐴 = ∫ = −𝐷𝐴𝐵 ∫ 𝑑𝑝
𝜋 𝑟1 𝑟2 − 𝑟1 2 𝑅𝑇 𝑝𝐴1 (𝑃 − 𝑝𝐴 ) 𝐴
[( ) 𝑧 + 𝑟1 ]
𝑧2 − 𝑧1
Diffusion Coefficients for Gases
Experimental determination of diffusion coefficients
 Evaporation of pure liquid in a narrow tube with a gas passed over the top
 Evaporation of a sphere for vapors of solids such as naphthalene, iodine, and
benzoic acid in a gas
 Two-bulb method, where sampling for 𝑐2 (𝑡) with the help of following relations
can be used to obtain diffusion coefficient
𝑐𝑎𝑣 − 𝑐2 𝐷𝐴𝐵 (𝑉1 + 𝑉2 )
= exp [− 𝑡]
𝑐𝑎𝑣 − 𝑐20 (𝐿⁄𝐴)(𝑉2 𝑉1 )
where,

𝑐1 + 𝑐2 = 𝑐10 + 𝑐20
𝑉1 𝑐10 + 𝑉2 𝑐20
𝑐𝑎𝑣 =
𝑉1 + 𝑉2
Experimental Diffusion Coefficients of Gases at P = 1 atm (CJG: Table 6.2-1)
Prediction of diffusion coefficients
For a binary pair of gases, the Chapman–Enskog correlation can be used (Eq. 6.2-44 in
C. J. Geankoplis):

1.8583 × 10−7 𝑇 3⁄2 1 1 1⁄2

𝐷𝐴𝐵 = 2 ( )( + )
𝜎𝐴𝐵 Ω𝐷,𝐴𝐵 𝑃 𝑀𝐴 𝑀𝐵

where, A and B are two kinds of molecules present in the gaseous mixture, 𝐷𝐴𝐵 is the
diffusivity (m2/s), T is the absolute temperature (K), M is the molar mass (kg/ kg mol),
P is the pressure (atm), and 𝜎 is the ‘average collision diameter’, Ω is a temperature-
dependent collision integral. Prediction accuracy of the above equation is about 8% up
to about 1000 K.

Another simpler correlation that can be used is (Eq. 6.2-45 in C. J. Geankoplis):

1⁄2
1.0 × 10−7 𝑇 3.5⁄2 1 1
𝐷𝐴𝐵 = ( ) ( + )
[(∑ 𝑣𝐴 )1⁄3 + (∑ 𝑣𝐵 )1⁄3 ]2 𝑃 𝑀𝐴 𝑀𝐵

where ∑ 𝑣𝐴 =sum of structural volume increments (Table 6.2-2, CJG).

It is clear from the above equation that temperature and pressure dependence of the
gas diffusivity is given by:

𝑇 3.5⁄2
𝐷𝐴𝐵 ∝( )
𝑃

𝐷𝐴𝐵2 𝑇2 1.75
=( )
𝐷𝐴𝐵1 𝑇1

𝐷𝐴𝐵2 𝑃1
=( )
𝐷𝐴𝐵1 𝑃2
Prediction accuracy of Fuller et al. Equation
Schmidt number for gases

𝜇 ⁄𝜌 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦
𝑁𝑆𝑐 = =
𝐷𝐴𝐵 𝑚𝑎𝑠𝑠 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦

 For gases, 𝑁𝑆𝑐 = 0.5– 2.0

 For liquid, , 𝑁𝑆𝑐 = 100– 10,000