LECTURE 4

MOLECULAR DIFFUSION IN LIQUIDS

• Equimolar counterdiffusion
• Diffusion of A through nondiffusing B
• Diffusion coefficients for Liquids
• Prediction of diffusivities of Electrolytes in
liquids
 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  DABC AV  X A1  X A2 
NA   , N A  NB
z2  z1 z2  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 
DABCav
x A1  x A2 , xBM 
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
DAB 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
of ethanol is 0.740 10 m / s . Calculate the steady-state flux N A .
2

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 / m3 z2  z1   0.002m

 2  988.1kg / m3
• 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
 xA1  xB1  1 xA2  xB 2  1
xB1  1  xA1 xB 2  1  xA2
 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
 20.07 kg / 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 / m3   988.1kg / m3 
    
  20.07kg / kgmol   18.798kg / kgmol 
2
 50.6kgmol / m3
xB 2  xB1 0.9723  0.9268 0.0455
xBM     0.949
In xB 2 / xB1  In0.9723 / 0.9268 0.04793

DABC 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
 Tutorial
• Problem 6.3-1 (Textbook, page 455)
 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 
VA1/ 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 m 2 / 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 m 2 / s
 Tutorial
• Problem 6.3-3 (Textbook, page 455)
• Problem 6.3-4 (Textbook, page 455)
Table 6.3-1
Table 6.3-2
Appendix A.2-4
PREDICTION OF DIFFUSIVITIES OF ELECTROLYTES IN LIQUIDS
• Electrolytes in aqueous solution such as KCI (potassium chloride)
dissociate into cations and anions.
• Each ion diffuses at a different rate.
• If the solution remain electrically 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.
• The value is in between the diffusivity values for the two ions.
• The well known Nernst-Haskell equation for dilute, single salt
solution can be use at 25°C to predict the overall diffusivity of the
salt A in the solvent B.
PREDICTION OF DIFFUSIVITIES OF ELECTROLYTES IN LIQUIDS
• Predict by Nernst – Haskell equation – for dilute, single salt solution

D
o
 8. 928  10 10
T
1 / n  1 / n 
AB
1 /   1 /  
Example: o
- 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
Table 6.3.3
PREDICTION OF DIFFUSIVITIES OF ELECTROLYTES IN LIQUIDS

• OR..predict by diffusion coefficient of an individual ion i at 25°C :

i
Di  2.662  10 7 Individual
ni
o n  n
D  Overall diffusivity
n / D  n / D
AB

• OR by correction factor.
o o
To correct D AB for NEW TEMP. (T), first calculate D AB at 25°C .
o
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 CaCl2 , 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 CaCl2 , 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
 Tutorial
• Problem 6.3-5 (Textbook, page 455)
• Problem 6.3-6 (Textbook, page 455)
 QUIZ 1
Problem 6.3-6 (Textbook, page 455)

Submission Date: 23 March 2018 (before 2pm)

LECTURE 5
MOLECULAR DIFFUSION IN SOLIDS
1. Diffusion in solids following Fick’s Law
- General equation for binary diffusion
- Concentration in solubility term
- Permeability equations for diffusion in solids.

2. Diffusion in porous solids that depends on

structure
- Diffusion of liquids in porous solids
- Diffusion of gases in porous solids.
Introduction
• Rates of diffusion of gases, liquids and solids are generally
slower in solid than rates in liquids and gases.
• BUT mass transfer in solid is important in chemical and
biological process.
• Examples:
 Drying of timber, salts and foods
 Diffusion and catalytic reaction in solid catalysts
 Separation of fluids by membranes
 Diffusion of gases through polymer films used in packaging
Introduction
• Classify transport in solids into two types of diffusion
1. Diffusion in solid following Fick’s law (does not depend on
actual structure of the solid)
2. Diffusion in porous solid (consider the actual structure and
void channels).
 MOLECULAR DIFFUSION IN SOLIDS
1. 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.
 Example:
 In leaching ;where the solid contains a large amount of water and a solute is
diffusing through this solution.
 Diffusing of water in food stuffs
 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
- since C A / C or x Ais 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   DAB  dC A
z1 C A1

N A z2  z1   DAB CA2  CA1 

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

NA
2L
 r

In r r2   DAB C A 2  C A1 
2L
N A  DAB C A1  C A 2 
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
- BUT 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 

• Convert to concentration in the solid, C A

 m3 
S  3 
CA   m solid .atm 
PA atm
 m 3

22.414 
 kgmol. A 
SPA  kgmolA 
  3  SI unit
22.414  m solid 
SPA  gmolA 
  3  cgs unit
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, CA1 at the inside surface of the rubber,

C A1 
SPA1

0.0510.01
 2.28 10 5 kgmolH 2

22.414 22.414 m3 solid

Since PA2 at the other side is 0, C A2  0
DAB C A1  C A 2 
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  PA2 1
NA 
22.414 L1 / PM 1  L2 / PM 2  ...
Table 6.5-1
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
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 A2 .
– The salt, in diffusing through the water in the void volume, takes a
tortuous path which is unknown and greater than (z₂-z₁) 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 in water
  = factor which corrects for the path
DAeff 

 2
DAB m / s  longer than z2  z1 
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
D
From Table 6.3.1, AB of KCI in water = 1.87  10 m 2
/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 
 Tutorial
• Problem 6.5-1 (Textbook, page 456)
• Problem 6.5-6 (Textbook, page 457)
Problem 6.5-1 (Textbook, page 456)
Problem 6.5-6 (Textbook, page 457)