LECTURE 3

MOLECULAR DIFFUSION IN LIQUIDS

➢ Liquid – liquid extraction/solvent extraction
➢ Gas absorption
➢ Distillation
➢ Oxygenation of rivers and lakes by air
➢ Diffusion of salts in blood
Equations for diffusion in liquids
✓ Since the molecules in a liquid are packed together much more
closely than gases, the density and resistance to diffusion much
more greater.
✓ Difference between diffusion in liquid and gases – the diffusivities
are often quite dependent on the concentration of the diffusing
components.
1) Equimolar counterdiffusion

DAB C A1  C A2  DAB C AV  X A1  X A 2 
NA   , N A  NB
z 2  z1 z 2  z1
NA  flux of A (kg mol A/s.m²)
D AB  diffusivity of A in B (m²/s)
C A1  the concentration of A in (kg mol A/m³) at point 1
X A1  the mole fraction of A at point 1
C AV  the average total concentration of A+B (kg mol/m³)
    1 2 
C AV        / 2
 M  av  M 1 M 2 
M 1  the average molecular weight at point 1 (kg mass/kg mol)
1  the average density of solution at point 1 (kg/m³)
2) Diffusion of A through nondiffusing B
✓ Solute A is diffusing and solvent B is stagnant/nondiffusing.
✓ E.g: - dilute solution of propionic acid (A) in a water (B) solution being
contacted with toluene.
- only propionic acid (A) diffuses through water phase, to the boundary
and then into the toluene phase.
- the toluene-water interface is a barrier to the diffusion of B, N B  0

P PA1 PBM
C AV  , C A1  , X BM 
RT RT P
xB 2  xB1
NA 
D AB Cav
 
x A1  x A 2 , x BM 
z 2  z1 xBM In  xB 2 / xB1 
x A1  xB1  x A 2  xB 2  1.0
*For dilute solutions xBM close to 1.0 and C is constant
D AB C A1  C A 2 
N 
z 2  z1
A
Example 6.3.1 (Diffusion of ethanol, A through water, B)
An ethanol (A) –water (B) solution in the form of a stagnant film 2D mm thick
at 293K is in contact at one surface with an organic solvent in which ethanol is
soluble and water is insoluble. Hence, N B  0. At point 1 the concentration of
ethanol is 16.8 wt% and the solution density is 1  972.8kg / m3 . At point 2,
the concentration of ethanol is 6.8 wt% and 2  988.1kg / m3 . The diffusivity
9 2
of ethanol is 0.74010 m / s . Calculate the steady-state flux N A .

DAB  0.740  109 m 2 / s At point 1 : wt% of ethanol is 16.8 wt%

M A  46.05(ethanol)
M B  18.02( water) At point 2 : 6.8 wt% of ethanol.

1  972.8kg / m 3 z2  z1   0.002m

 2  988.1kg / m 3
• Mole fraction of ethanol at point 1 and 2 (using 100 kg of solution) :
 16.8kg 
 
x A1   46.05kg / kgmol 
 16.8kg   83.2kg 
    
 46.05kg / kgmol   18.02kg / kgmol 
0.3648kgmol

4.9819kgmol
 0.0732
 6.8kg 
 
x A2   46.05kg / kgmol 
 6.8kg   93.2kg 
    
 46.05kg / kgmol   18.02kg / kgmol 
0.1477kgmol

5.3197kgmol
 0.0277
 x A1  xB1  1 x A 2  xB 2  1
xB1  1  x A1 xB 2  1  x A 2
 1  0.0732  1  0.0277
 0.9268  0.9723
To calculate the average molecular weight at point 1 and 2:
100kg
M1 
 16.8kg   83.2kg 
    
 46.05kg / kgmol   18.02kg / kgmol 
100kg

4.9819kgmol
 20.07kg / kgmol
100kg
M2 
 6.8kg   93.2kg 
    
 46.05kg / kgmol   18.02kg / kgmol 
100kg

5.3197kgmol
 18.798kg / kgmol
  1  2 
C AV     / 2
 M1 M 2 
 972.8kg / m 3   988.1kg / m 3 
    
  20.07kg / kgmol   18.798kg / kgmol 
2
 50.6kgmol / m 3
xB 2  xB1 0.9723  0.9268 0.0455
xBM     0.949
In xB 2 / xB1  In 0.9723/ 0.9268 0.04793

DAB C AV  x A1  x A 2 
NA 
z2  z1 xBM

0.740 10 50.60.0732  0.0277
9

0.0020.949
 8.99 107 kgmol / s.m 2
 DIFFUSION COEFFICIENTS FOR LIQUIDS
• Table 6.3.1 (Diffusion coefficients for dilute liquid solutions)
• Prediction :
1) Wilke-Chang correlation:

DAB  1.17310 16

OM B 
1/ 2 T
0.6
M BVA
MB
= the molecular weight of solvent B
B = viscosity of solvent (Pa·s or kg/m.s)
VA = solute molar volume at the boiling point (Table 6.3.2)
O = an association parameter of the solvent

water = 2.6 benzene = 1.0

methanol = 1.9 ether = 1.0
ethanol = 1.5 heptane = 1.0
others = 1.0
 2) Stokes – Einstein equation:

9.96 1016 T
DAB 
VA 1/ 3

*When VA is above 0.5 m³/kg mol, this equation should be used.

Example 6.3.2 (Prediction of liquid diffusivity)

Predict the diffusion coefficient of acetone (CH₃COCH₃) in water at 25°C and
50°C using Wilke – Chang equation. The experimental value is 1.28109 m2 / s
at 25°C.
Solution:
- From Appendix A.2.4, viscosity of water at 25°C, B  0.893710 Pa.s
3

and at 50°C, B  0 .5494 10 3

Pa.s
• From Table 6.3.2,
C H O
    
VA  14.8 103 3  3.7 103 6  7.4 103 1 
 0.0740m3 / kgmol
For water, the association parameter O= 2.6 and M B  18.02kg / kgmol
At T=25°C (298K) :
DAB  1.17310 16
O B 
1/ 2 T
 BVA0.6
1.1731016 2.6 18.02 298
1/ 2

 
0.8937103 0.0740
0.6

 1.277 109 m 2 / s
At T=50°C (323K) :
1.1731016 2.6 18.02 323
1/ 2

 
DAB
0.5494103 0.0740
0.6

 2.251109 m2 / s
PREDICTION OF DIFFUSIVITIES OF ELECTROLYTES IN LIQUIDS
• Electrolytes in aqueous solution such as KCI dissociate into cations and anions.
• If the solution remain neutral, the cations and anions diffuse effectively as one
component and the ions have the same net motion or flux.
• Hence, the average diffusivity of the KCI is a combination of the diffusion coefficient of
the two ions.
• Nernst – Haskell equation – for dilute, single salt solution
o
D AB  8.92810 10
T
1 / n  1 / n 
Example: o 1 /   1 /  
- KCI D = diffusivity (cm²/s)
AB

- NaoH n = the valence of the cation

- LaCI₃ n = the valence of the anion
- CaCI₂  and = limiting ionic conductance (A/cm²)(V/cm)(g equiv./ cm²)
= Table 6.3.3
The diffusion coefficient of an individual ion I at 25°C :
i
Di  2.662  107
ni
o n  n
D 
n / D  n / D
AB
 o o o
• To correct D AB for temp., first calculate D AB at 25°C . Then multiply this D AB
at 25°C by T/ 334w  , where  w is the viscosity of water in cp at the new T
(Appendix A.2.4)

Example 6.3.3 (Diffusivities of electrolytes)

Predict the diffusion coefficient of dilute electrolytes for the following cases:
o
a) For KCI at 25°C, predict D AB
b) Predict the value for KCI at 18.5°C. The experimental value is 1.7 105 cm 2 / s
c) For CaCl 2 , predict DAB at 25°C. Also predict Di of the ion Ca 2 and Cl 
Solution:
a) From Table 6.3.3, ( K  )  73.5 and (Cl  )  76.3
o 8.9281010 T 1 / n  1 / n 
D AB 
1 / n  1 / n 
8.9281010 298.21 / 1  1 / 1

1 / 73.5  1 / 76.3
 1.993105 cm 2 / s
b) For T=18.5° (291.7K)
,  w  1.042cp  App. A.2.4 
T
Correction factor 
334 w 
291.7

334 1.042
 0.8382
o o
D AB 185C   0.8382D AB 25C 

 0.8382 1.993105 
 1.671105 cm 2 / s

c) For CaCl 2 , from Table 6.3.3:

 Ca 2 
    
  59.5,  Cl   76.3
 2 
n  2, n  1
o 8.9281010 298.21 / 2  1 / 1
D AB 
1 / 59.5  1 / 76.3
 1.335105 cm 2 / s
• To calculate the individual ion diffusivities at 25°C,
i
Di  2.662  107
ni

Dca 2  2.662  107
n

 2.662  10 7
59.5
2
 0.792  105 cm 2 / s

DCl   2.662 107
n
 2.662  107
76.3
1
 2.031 105 cm 2 / s
o n  n
DAB 
n / D  n / D
2 1

  
1 / 0.792 105  2 / 2.031105 
 1.335105 cm 2 / s
LECTURE 4
 MOLECULAR DIFFUSION IN SOLIDS
➢ Drying of timber, salts and foods
➢ Diffusion and catalytic reaction in solid catalysts
➢ Separation of fluids by membranes
➢ Diffusion of gases through polymer films
Diffusion in solids following Fick’s Law
▪ does not depend on the actual structure of the solid
▪ diffusion occurs when the fluid or solute diffusing is actually dissolved in the
solid to form a more or less homogenous solution.
▪ general equation for binary diffusion:
N A  CDAB
dx A C A
 N A  NB 
dz C
- bulk flow term, (C A / C )(N A  NB ) is usually small
- sinceC A / C or x A is quite small. Hence, it is neglected. Also C is assumed
constant:
DAB dC A , DAB = diffusivity in m²/s of A through B
N 
A
dz DAB  DBA
• Integrate:
z2 CA2

N A  dz   D AB  dC A
z1 C A1

N A z2  z1    DAB C A2  C A1 
DAB C A1  C A2 
NA 
z2  z1 
• For the case of diffusion radially through a cylinder wall of inner radius r₁, and
outer r₂ and length L
NA dCA
  DAB
2rL dr
Integrate:
r2 A2 C
NA 1
2L r r dr   DAB C dC A
1 A1

NA
2L
 r

In r r2   D AB C A 2  C A1 
2L
N A  DAB C A1  C A2 
1

 r2   r2 
In    DAB C A1  C A 2 
NA
In 
2L  r1   r1 
• The diffusion coefficient, DAB in the solid is not dependent upon the pressure
of the gas/liquid on the outside of the solid.
• E.g: - if CO₂ gas is outside a slab of rubber and is diffusing through the rubber,
DAB would be independent of P , the partial pressure of CO₂ at surface.
A
- the solubility of CO₂ in the solid is directly proportional to PA .

 m3 solute 
• The solubility of a solute gas (A) in a solid, S  3 
 m solid.atm 

Concentration in the solid, C A

 m3 
S  3 
CA   m solid.atm 
PA atm
 m 3

22.414 
 kgmol. A 
SPA  kgmolA 
  3 
22.414  m solid 
SPA  gmolA 
  3 
22414  cm solid 
Example 6.5.1
The gas hydrogen at 17°C and 0.01 atm partial pressure is diffusing through a
membrane of vulcanized neoprene rubber 0.5mm thick. The pressure of H₂ on
the side of the rubber 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
rubber at 17°C is 0.051 m³/m³solid.atm and the diffusivity, DAB is 1.031010 m2 / s
at 17°C.
Solution:
The equilibrium concentration, C A1 at the inside surface of the rubber,

C A1 
SPA1

0.0510.01 kgmolH2
 2.28 105 3
22.414 22.414 m solid
Since PA 2 at the other side is 0, C A2  0
DAB C A1  C A2 
NA 
z2  z1 

1.0310 2.2810
10 5
0 
0.0005m
 4.69 1012 kgmolH2 / s.m 2
• Permeability equations for diffusion in solids.
– In many cases for diffusion of gases in solids are not given as diffusivities
and solubilities but as permeabilities, PM in m³ of solute gas A diffusing per
second per m² cross-sectional area through a solid 1 m thick under 1 atm
pressure.
DAB C A1  C A 2 
NA 
z 2  z1
S PA1 S PA 2
C A1  , C A2 
22.414 22.414
DAB S PA1  PA 2 
NA 
22.414z 2  z1 
P P  P  m3 STP 
 M A1 A2 , PM  DAB S
22.414z2  z1  s.m 2C.S .atm / m
– When there are several solid in series and L₁, L₂,… represent the thickness
of each:
PA1  PA 2 1
NA 
22.414 L1 / PM 1  L2 / PM 2  ...
Example 6.5.2
A polyethylene film 0.00015 m (0.15mm) thick is being considered for use in
packaging a pharmaceutical product at 30°C. If the partial pressure of O₂
outside the package is 0.21 atm and inside it is 0.01 atm, calculate the
diffusion flux of O₂ at steady state. Use permeability data from Table 6.5.1.
Assume that the resistances to diffusion outside the film and inside are
negligible compared to the resistance of the film.
Solution: 3
12 m solute
From Table 6.5.1, M P  4.17  10 2
s.m .atm / m
PM PA1  PA 2 
NA 
22.414 z 2  z1 


4.17 10 0.21 0.01
12

22.4140.00015 0
 2.480 1010 kgmol / s.m 2
Diffusion in porous solids that depends on structure
1. Diffusion of liquids in porous solids
– In this section we are concerned with porous
solids that have pores or interconnected voids
in the solid which affect the diffusion.
– For the situation where the voids are filled
completely with liquid water, the concentration
of salt in water at boundary 1 is C A1 and at point 2 is C A 2 .
– The salt, in diffusing through the water in the void volume, takes a
tortuous path which is unknown and greater than (2₂-2₁) by a factor ,
called tortuosity.
– For a dilute solution for diffusion of salt in water at steady-state,

DAB C A1  C A2   = open void fraction

NA 
 z2  z1  DAB = diffusivity ofsalt
z 2  z1 
in water
  = factor which corrects for the path
DAeff 

 2
DAB m / s  longer than
Example 6.5.3
A sintered solid of silica 2.0 mm thick is porous, with a void fraction  of 0.30

and a turtuosity of 4.0. The pores are filled with water at 298 K. At one face
the concentration of KCI is held at 0.10 g mol/liter and fresh water flows
rapidly past the other face. Neglecting any other resistance but than in the
porous solid, calculate the diffusion of KCI at steady-state.
Solution:
9 2
D
From Table 6.3.1, AB of KCI in water = 1.87  10 m /s
C A1 = 0.1 g mol/liter
= 0.1 kg mol/m³
C A2 = 0
DAB C A1  C A 2 
NA 
  z 2  z1 


 
0.3 1.870 109 0.1  0
40.002  0
 7.01109 kg mol KCI / s.m 2
2. Diffusion of gases in porous solids.

DAB C A1  C A 2 
NA 
  z 2  z1 
DAB PA1  PA 2 

RT  z 2  z1 