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EAT 347/4: MASS TRANSFER

CHAPTER 2: MASS TRANSPORT

PROCESSES (part 2)

SARA YASINA BINTI YUSUF,

PhD, AMIChemE
SEMESTER 1, 2019
 CONTENT (week 4)

4. Molecular Diffusion in Liquids

• Equations for Diffusion in Liquids
• Diffusion Coefficients for Liquids
5. Diffusion of Biological
• Prediction of Diffusivities in Liquids Solutions and Gels
• Diffusion of Biological Solutes in
Liquids
• Diffusion in Biological Gels

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4. Molecular Diffusion
in Liquids

• Equations for Diffusion in Liquids

• Diffusion Coefficients for Liquids
• Prediction of Diffusivities in Liquids
 Molecular Diffusion in Liquids

Distillation

Liquid-liquid extraction or
solvent extraction

Gas absorption
Nature: diffusion of salts in blood
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 Molecular Diffusion in Liquids

• Rate of molecular diffusion is slower than in gases (gas is 105

times greater)
• Concentrations in liquids are considerably higher than in gases
→ flux in gas is only 100 times faster
• Density and the resistance to diffusion are much greater in
liquid rather than gas

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 Equations for Diffusion in Liquids

A. Equimolar Counter-Diffusion (EMD)

NA =
(
D AB c A1 − c A2 ) = DAB cav (x A − x A )
1 2

z 2 − z1 z 2 − z1

Average concentration relates to density of liquids via:

      
cav =   =  1 + 2  2
 M  av  M 1 M 2 

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 Equations for Diffusion in Liquids

B. Diffusion of A through non-diffusing B or Unimolecular

Diffusion (UMD)
NA =
D AB cav
(z 2 − z1 )x BM
(
x A1 − x A2 )
x B2 − x B1 𝑥𝐴1 + 𝑥𝐵1 = 𝑥𝐴2 + 𝑥𝐵2 =1
x BM =
(
ln x B2 x B1 )
For solute solution, xBM is close to 0, therefore:

NA =
(
D AB c A1 − c A2 )
z 2 − z1
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 Example 2.9

An ethanol (A) – water(B) solution in the

form of a stagnant film 2.0 mm thick at
293K 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 ρ1 = 972.8 kg/m3. At point 2 the
concentration of ethanol is 6.8 wt% and
ρ2 = 988.1 kg/m3. The diffusivity of ethanol
is 0.740 X 10-9 m2/s. Calculate the steady-
state flux NA.

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 Diffusion Coefficients for
Liquids

Experimental
Experimental liquid
determination of
diffusivities data
diffusivities

N A = D AB =
c − c Table

6.3-1
c0 − c0 2A
(dilute
=
ln
c − c V
D AB t
solutions)
D AB  DBA

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 Prediction of Diffusivities Assumption/condition:
• Applies well to very large unhydrated,
in Liquids sphere-like solute molecules
• VA above abt 0.500 m3/kg mol

Can be presented in semi-empirical equations:

9.96  10 −16 T Molar volume at its normal
Viscosity of solution (Pa·s) D AB = boiling point (m3/kg mol)
V A1 3

For a very large spherical molecule A diffusing in a liquid

solvent B → Stokes-Einstein equation (Stokes’- drag on
the moving solute molecule)

Modification to the equation, assuming that all

molecules are alike and arranged in a cubic lattice, and
by expressing molecular radius in terms of molar volume

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 Prediction of Diffusivities in Liquids

• For smaller solute molar volume,

semi theoretical expressions, Wilke-
Chang correlation (solute A dilutes
in solvent B)
T
D AB = 1.173  10 −16
(M B )
12
 BV A0.6
Association parameter of Viscosity
solvent of B (Pa·s)

Molar weight of Solute molar volume at its

solvent B normal boiling point (m3/kg
mol)

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 Example 2.10

Predict the diffusion coefficient of acetone (CH3COCH3) in water at

25oC and 50oC using the Wilke-Chang equation. The experimental
value is 1.28 x 10-9 m2/s at 298K

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5. Diffusion of
Biological Solutions and
Gels
• Diffusion of Biological Solutes in
Liquids
• Diffusion in Biological Gels
 Diffusion of Biological Solutes in Liquids

• Drying of liquid solutions of fruit juices, coffee and tea → Water,

volatile aroma or flavour are removed
• Fermentation processes → nutrients, sugar, oxygens diffuse to
microorganisms wastes product
enzymes

• Colloids → macromolecules in solution having molecular weights

of ten of thousands or more
• Interaction and binding in diffusion

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 Diffusion of Biological Solutes in
Liquids

• Experimental data
for biological
solutes

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 Diffusion of Biological Solutes in
Liquids

Prediction of diffusivities for biological solutes

• For MW < 1000, Stokes’-Einstein equation :

9.96 × 10−16 𝑇
𝐷𝐴𝐵 = 1 Τ3
𝜇𝑉𝐴 Molar volume at its normal
Viscosity of solution (Pa·s) boiling point (m3/kg mol)

• For MW > 1000, Polson equation:

9.40 × 10−15 𝑇
𝐷𝐴𝐵 = Molecular weight of the
𝜇 𝑀𝐴 1Τ3 large molecule A

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 Example 2.10

Predict the diffusivity of bovine serum albumin at 298 K in water as

a dilute solution using the modified Polson equation and compare
with the experimental value.

9.40 × 10−15 𝑇
𝐷𝐴𝐵 =
𝜇 𝑀𝐴 1Τ3

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 Diffusion of Biological Solutes in
Prediction of diffusivities of small solutes in Liquids

protein solution

• When a small solutes diffuse in macromolecule (P) protein solution,

diffusivity DAB cannot be used because of the blockage to diffusion
by the large molecule. Therefore, DAP can be calculated as:
kgP/m3
𝐷𝐴𝑃 = 𝐷𝐴𝐵 1 − 1.81 × 10−3 𝑐𝑃

• The diffusion equation:

𝐷𝐴𝑃 𝑐𝐴1 − 𝑐𝐴2
𝑁𝐴 =
𝑧2 − 𝑧1

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 Diffusion of Biological Solutes in
Liquids

Prediction of diffusivities with binding present

• When a small solutes diffuse in macromolecule (P) protein

solution, diffusivity DAB cannot be used because of the blockage
to diffusion by the large molecule. Therefore, DAP can be
calculated as:

% free A % bound A
𝐷𝐴𝑃 = 𝐷𝐴𝐵 1 − 1.81 × 10−3 𝑐𝑃 + 𝐷𝑃
100 100

Diffusivity of protein alone

in the solution

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 Diffusion in
Biological Gels

• Gels can be looked

upon as semisolids
materials which are
porous
• Composed of
macromolecules (in
dilute aqueous
solution) with the gel
comprising of wt % of
water solution

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 Example 2.11

A tube or bridge of a gel solution of 1.05 wt % agar in water at 278 K

is 0.04 m long and connects two agitated solutions of urea in water.
The urea concentration in the first solution is 0.2 g mol urea per
liter solution and 0 in the other. Calculate the flux of urea in
kg-mol/m2∙s at steady-state

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Next: Chapter 2
Part 3