Transport phenomena

DIFFUSIVITY AND THE MECHANISMS OF MASS TRANSPORT

Teknik Kimia Universitas Pertamina for Teknik Perminyakan Universitas Pertamina - 2018
DIFFUSIVITY AND CONTENT
Laws of molecular transport
THE


 Temperature & pressure dependence of

MECHANISMS diffusivities
Estimation of diffusivity for gases & liquid
OF MASS 

TRANSPORT
OBJECTIVE
 Able to estimate the effect of pressure
and temperature to diffusivities
 Able to use data on appendix to estimate
diffusivity of fluids
Diffusion & Diffusivity
Diffusion (phenomena)
𝑥𝐴

 Molecular transport of one substance relative

to another, because of a concentration
gradient

𝜔𝐴𝑦 (mass flow of A in y-direction)

∆𝑥𝐴 𝑥𝐴 = 𝑥𝐴0
∝ A(area) ∝ 𝑌
(concentration gradient)

𝜔𝐴𝑦 𝑑𝑥𝐴 𝑥𝐴
= 𝑗𝐴𝑦 = −𝜌𝒟𝐴𝐵
𝐴 𝑑𝑦

Diffusivity (diffusion coefficient), 𝒟𝐴𝐵 𝑥𝐴 (𝑦)

 Proportional factor between mass flux (𝑗𝐴𝑦 )

𝑑𝑥 𝑥𝐴
and concentration gradient ( 𝑑𝑦𝐴 ) 𝑥𝐴 = 𝑥𝐴0

Maximum solubility of A in B
Laws of Molecular Transport
 Newton’s law of viscosity
𝐹 𝑑𝑣𝑥
𝜏𝑦𝑥 = = −𝜇
𝐴 𝑑𝑦

 Fourier’s law of heat conduction

𝑄 𝑑𝑇
𝑞𝑦 = = −𝑘
𝐴 𝑑𝑦
 Fick’s law of binary diffusion Mass fraction of A
𝜔𝐴𝑦 𝑑𝑥𝐴
𝑗𝐴𝑦 = = −𝜌𝒟𝐴𝐵 Concentration gradient
Molecular mass-flux 𝐴 𝑑𝑦
All of the above equation is written for one-dimensional flow
Temperature &
Pressure Dependence
of Diffusivity
For gases at low density
 Diffusivity 𝒟𝐴𝐵 increases with
increasing T
 Varies inversely with P
 Is almost independent of the
composition for a given gas
pair
Temperature &
Pressure Dependence
of Diffusivity
For gases at low density
 Diffusivity 𝒟𝐴𝐵 increases with
increasing T
 Varies inversely with P
 Is almost independent of the
composition for a given gas
pair
Temperature & Pressure
Dependence of
Diffusivity

For liquid
 Diffusivity 𝒟𝐴𝐵 generally
increases with increasing T
 Is strongly composition
dependent
Estimation of 𝒟𝐴𝐵 for Binary Gas
Mixtures
At low pressure
1. Developed by JC. Slattery and RB. Bird
𝑏
𝑝𝒟𝐴𝐵 𝑇
1Τ3 5Τ12 1Τ2
=𝑎
𝑝𝑐𝐴 𝑝𝑐𝐵 𝑇𝑐𝐴 𝑇𝑐𝐵 1Τ𝑀𝐴 + 1Τ𝑀𝐵 𝑇𝑐𝐴 𝑇𝑐𝐵

𝒟𝐴𝐵 = diffusivity, cm2/s 𝑇𝑐 = critical temperature, K

𝑝 = pressure, atm 𝑝𝑐 = critical pressure, atm
𝑇 = temperature, K 𝑀 = molecular weight
Estimation of 𝒟𝐴𝐵 for Binary Gas
Mixtures
At low pressure
1. Developed by JC. Slattery and RB. Bird
𝑏
𝑝𝒟𝐴𝐵 𝑇
1Τ3 5Τ12 1Τ2
=𝑎
𝑝𝑐𝐴 𝑝𝑐𝐵 𝑇𝑐𝐴 𝑇𝑐𝐵 1Τ𝑀𝐴 + 1Τ𝑀𝐵 𝑇𝑐𝐴 𝑇𝑐𝐵

For non-polar gas pairs (excl. He & H2): For a pair of H2O and non-polar gas:
(dimensionless) (dimensionless)
𝑎 = 2.745 x 10-4 𝑎 = 3.640 x 10-4
𝑏 = 1.823 𝑏 = 2.334

At atmospheric pressure, this estimation gives an average deviation of 6-8%

Exercise
Prediction of a low-density binary diffusivity
Estimate 𝒟𝐴𝐵 for the system methane-ethane at 293K and 1
atm by the method developed by JC. Slattery and RB. Bird

𝒟𝐴𝐵 = 0.152 cm2/s

Estimation of 𝒟𝐴𝐵 for Binary Gas Mixtures
At low pressure
2. Chapman-Enskog kinetic theory
1 1 1
𝑐𝒟𝐴𝐵 = 2.2646 × 10−5 𝑇 +
𝑀𝐴 𝑀𝐵 𝜎𝐴𝐵 2 Ω𝒟,𝐴𝐵
𝑐 = molar density, g-mole/cm3
𝑛 𝑝
For ideal gas: 𝑐= =
𝑉 𝑅𝑇
Hence, the equation become:

1 1 1
𝒟𝐴𝐵 = 1.8583 × 10−3 𝑇3 +
𝑀𝐴 𝑀𝐵 𝑝𝜎𝐴𝐵 2 Ω𝒟,𝐴𝐵
Estimation of 𝒟𝐴𝐵 for Binary Gas Mixtures
At low pressure
2. Chapman-Enskog kinetic theory
For ideal gas:
1 1 1
𝒟𝐴𝐵 = 1.8583 × 10−3 𝑇3 +
𝑀𝐴 𝑀𝐵 𝑝𝜎𝐴𝐵 2 Ω𝒟,𝐴𝐵

𝒟𝐴𝐵 = diffusivity, cm2/s 𝑀 = molecular weight

𝑝 = pressure, atm 𝜎= collision diameter, 𝐴ሶ
𝑇 = temperature, K Ω = collision integral for diffusion
(dimensionless)
Ω𝒟,𝐴𝐵 is available in Table E.2 of Bird, as a function of 𝐾𝑇/𝜀𝐴𝐵
Table E.2
Collision
integrals as a
function of
KT/𝜀𝐴𝐵
Estimation of 𝒟𝐴𝐵 for Binary Gas Mixtures
At low pressure
2. Chapman-Enskog kinetic theory
The values of 𝜎 and 𝜀 are for gas pairs.
For non-polar gas pairs may estimated by:
1
𝜎𝐴𝐵 = 𝜎𝐴 + 𝜎𝐵 𝜀𝐴𝐵 = 𝜀𝐴 𝜀𝐵
2
𝜎𝐴 = collision diameter of compound A, 𝐴ሶ
𝜎𝐵 = collision diameter of compound B, 𝐴ሶ
𝜀 = Lennard-Jones parameter

Estimation of 𝒟𝐴𝐵 for binary mixtures of non-polar gases with this method is
accurate within 5%
Estimation of 𝒟𝐴𝐵 for Binary Gas Mixtures
At low pressure
2. Chapman-Enskog kinetic theory
 When σ and ε/K of the compound is not available, they may be
approximated by empirical relations:

Data required ε/K (in K) σ (in 𝐴)ሶ

1 Τ3 1Τ3
Fluids Critical properties ε/K = 0.77 Tc σ = 0.841 𝑉෨𝑐 or σ = 2.44 𝑇𝑐
ൗ𝑃𝑐
T = temperature, K
σ = collision diameter, 𝐴ሶ
𝑉෨𝑐 = molar specific volume at critical point, cm3/gmole
P = presure, atm

 Then, 𝜎AB and 𝜀 AB for the gas pair are calculated the same way as
before
Exercise
Prediction of a low-density binary diffusivity
Estimate 𝒟𝐴𝐵 for the system methane-ethane at 293K and 1 atm
based on the Chapman-Enskog kinetic theory
a. Using Lennard-Jones parameter data from appendix E
b. With the Lennard-Jones parameter estimated from critical
property data

a. 𝒟𝐴𝐵 = 0.146 cm2/s b. 𝒟𝐴𝐵 = 0.138 cm2/s

Estimation of 𝒟𝐴𝐵 for Binary
Gas Mixtures
3. Reduced self-diffusivity chart
To use this chart for binary diffusion of
chemically dissimilar species:

𝑇𝑐 = 𝑇𝑐𝐴 𝑇𝑐𝐵 𝑝𝑐 = 𝑝𝑐𝐴 𝑝𝑐𝐵

𝑐𝒟𝐴𝐵
𝑐𝒟𝐴𝐵 𝑟 = ൗ 𝑐𝒟
𝐴𝐵 𝑐

𝑇𝑐 = critical T, K
𝑝𝑐 = critical pressure, atm
𝑐 = molar concentration, gmole/cm3
𝑐𝒟𝐴𝐵 𝑟 = reduced property of 𝑐𝒟𝐴𝐵
Estimation of 𝒟𝐴𝐵 for Binary
Gas Mixtures
3. Reduced self-diffusivity chart
The critical diffusivity data 𝑐𝒟𝐴𝐵 𝑐 can be
obtained from
 Data at other P & T
 Estimated from
1/2
1 1 𝑝𝑐𝐴 𝑝𝑐𝐵 1/3
𝑐𝒟𝐴𝐵 𝑐 = 2.96 × 10−6 +
𝑀𝐴 𝑀𝐵 𝑇𝑐𝐴 𝑇𝑐𝐵 1/12
• At low P, above equation is accurate

Can be used to estimate diffusivity at higher P,

but the result should be regarded as provisional
Exercise
Estimation of Binary Diffusivity at High Density
Estimate 𝑐𝒟𝐴𝐵 for a mixture of 80 mole% CH4 and 20 mole% C2H6 at
136 atm and 313K. It is known that, at 1 atm and 293K, the molar
density is c = 4.17 X 10-5 g-mole/cm3 and 𝒟𝐴𝐵 = 0.163 cm2/s.

Try the 2 available methods to obtain 𝑐𝒟𝐴𝐵 𝑐

From data of appendix: From estimation:

𝑐𝒟𝐴𝐵 = 7.3 x 10-6 gmole/cm.s 𝑐𝒟𝐴𝐵 = 6.2 x 10-6 gmole/cm.s
Estimation of 𝒟𝐴𝐵 for Binary Liquid Mixtures
Empirism is used, no satisfacoty theory of diffusion available for liquid
1. Wilke-Chang equation

For small concentration of A in B

𝑉෨𝐴 = molar volume of solute A, cm3/gmole

−8
𝜑𝐵 𝑀𝐵 𝑇 𝜇= viscosity of the solution, cp
𝒟𝐴𝐵 = 7.4 × 10
𝜇 𝑉෨𝐴0.6 𝜑𝐵 = association parameter for the solvent
T = temperature, K

Recommended values of 𝜑𝐵 : • 2.6 for water

• 1.9 for methanol
• 1.0 for benzene, ether, heptane, etc

For dillute solutions of non-dissociating molecules, accuracy is within 10%

Exercise
Estimation of liquid diffusivity
Estimate the diffusivity for a dilute aqueous solution of acetic acid at
12.5oC, using the Wilke-Chang equation.
The viscosity of of the solution is 1.22 cp, 𝑉෨𝐴 = 64.1 cm3/gmol.

𝒟𝐴𝐵 = 9.8 x 10-6 cm2/s

Reference
 Bird, R. B., Stewart W. E., Lightfoot, E. N., “ Transport
Phenomena” 2nd ed., John Wiley & Sons, USA, 2007.