Diffusion Coefficient – Transport Proceses II

Gas Mass Diffusivity

- Simple, low density gaseous mixtures

Sutherland, Jeans, Chapman and Cowling

Self diffusion coefficient

Where
DAA* = diffusion coefficient (cm2/s)
MA= molecular weight (g/mol)
N= Avogadro´s number= 6.022x1023 molecules/mol
P= system pressure (atm)
T= absolute temperature (K)
K = Boltzman cte = 1.38 x 10-16 ergs/K
σAB= Lennar-Jones diameter of spherical molecules (Å)

Binary mixture

Hirschfelder – For non-polar and non-reacting; modern- better approximations – considers to

some certain extent interaction

Where:
ΩD= collision integral (dimensionless)
σAB= collision diameter - Lennar-Jones (Å)

1
εAB= energy molecular interaction (ergs)

When values not available:

To get average values

To extrapolate data:

Fuller, Schettler, Giddings – when collision diameter and energy molecular interaction parameters
not available (still non-polar, low P). Use table 24.3.

Where
DAB = diffusion coefficient (cm2/s)
T in K
P in atm
v= structural diffusion volume increments + atomic diffusion volume increments

Brokow – binary gas mixture BUT polar components

Apply Hirschfelder BUT collision integral :

1
𝛿𝐴𝐵 = (𝛿𝐴 𝛿𝐵 )2 (24-44b)

2
Where
μD = dipole moment (Debye)
Vb = liquid molear volume at boiling point (cm3/gmol)
Tb = temp at boiling point (K)

T* = kT/ εAB (24-45b)

Where
A= 1.060 E= 1.035
B= 0.156 F=1.529
C=0.193 G=1.764
D=0.476 H=3.894

Gas mixture

Where
D1-mixture = Mass diffusivity for component 1 in the gas mixture
D1-n = Diffusivity for binary pair 1 through n
y´n = mole fraction of component n in the gas mixture, evaluates on component 1-free basis.

𝑦2 𝑦2
𝑦2´ = 𝑦 = (24-49b)
2 +𝑦3 + ...𝑦𝑛 1−𝑦1

Liquid Mass Diffusivity

Wilke and Chang

Where
DAB = diffusion coefficient A in liq. solvent B (cm2/s)
μB= viscosity of B (cp)
T= absolute temperature (K)
VA = molecular volume of solute at boiling point (cm3/g mol)

3
ΦB= association parameter for B

Tylus and Calus – when data not available

𝑉𝐴 = 0.285 𝑉𝑐1.048 (24-52b)
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Vc = critical volume (cm /g mol)
Hyduk and Laudie - infinite dilution, non-electrolytes, in water

Where
DAB = diffusion coefficient A in liq. solvent B (cm2/s)
μB= viscosity of B (cp)
VA = molecular volume of solute and boiling point (cm3/g mol)

Scheibel – recommended for organic solvents

Except:
1. Benzene as solvent, if VA < 2 VB, use K=18.9 x 10-8
2. Other org. solvents, if VA < 2.5 VB, use K=17.5 x 10-8

Vignes – for concentrated solutions (but not alcohols), at ambient T

𝐷𝐴𝐵𝑐 = (𝐷𝐴𝐵𝑑 )𝑥𝐵 (𝐷𝐵𝐴𝑑 )𝑥𝐴 (24-55a)

Leffer and Cullinan – for concentrated solutions, at ambient T

𝐷𝐴𝐵𝑐 𝜇 = (𝐷𝐴𝐵𝑑 𝜇𝐵 )𝑥𝐵 (𝐷𝐵𝐴𝑑 𝜇𝐴 )𝑥𝐴 (24-55b)

Tyne – Correction for T

𝐷𝐴𝐵 𝑇1 𝑇𝑐 −𝑇2 𝑛
( )=( ) (24-55a)
𝐷𝐴𝐵 𝑇2 𝑇𝐶 −𝑇1

Where n  related to latent heat of vaporization of the solvent at boiling point

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Nernts –Einstein – for electrolytes

Where
DAB = diffusion coefficient (cm2/s)
R- gas cte = 8.316 J/K gmol
T- K
λ°+= positive limiting ionic conductance (amp/cm2)
λ°-= negative limiting ionic conductance (amp/cm2)
F = Faraday´s cte – 96,500 coulombs/g equivalent

Solid Mass Diffusivity

Where:
D0 = proportionality cte (cm2/s)
Q = activation energy for transfer to occur (J/mol)
R = thermodynamic cte= 8.314 J/mol K
T=K
Below- bcc- body centered cubic surface; fcc = face centered body surface

Table 24.6 Data of self diffusion in pure metals

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 Table 24-7 Diffusion parameters common substitutional dopants in polycrystalline silicon

Table 24.8 Diffusion parameters for interstitial solutes in iron

Convective mass transfer across interface

Where
NA = molar flux at fixed spatial coordinates
kc= convective-mass transfer coefficient
ΔCA= Concentration difference between boundary and surface concentrations

Reference

 Welty, R. J., Wicks, C. E., Wilson, R. E., Rorrer, G. L., Fundamentals of Momentum, Heat, and Mass
Transfer, 5th or 6th Edition., John Wiley and Sons, 2008/2005