Lecture 3-Diffusion in

dilute solutions
Dr. Emad Alhseinat

CHEG324: Mass Transfer

Diffusion:
• What is Diffusion?
– process by which molecules, ions, or other small particles
spontaneously mix, moving from regions of relatively high
concentration into regions of lower concentration
• How to study diffusion?
– Scientific description: By Fick’s law and a diffusion
coefficient (D-model)
– Engineering description: By a mass transfer coefficient (K-
model)
Models for diffusion
• Mass flux:
amount of gas removed
carbon dioxide flux 
(time)(unit area)

• Two models (from assumptions!)

– Fick’s law

 carbon dioxide concentration difference 

carbon dioxide flux  D  
 capillary length 
– Mass transfer coefficient model
carbon dioxide flux  k carbon dioxide concentration difference 
Diffusion in dilute solutions
• Diffusion in dilute solutions are frequently encountered
– diffusion in living tissue almost always involves the transport of small amounts of
solutes like salts, antibodies, enzymes, or steroids.
• Two cases are studied
– steady-state diffusion across a thin film
• basic to membrane transport
– unsteady-state diffusion into a infinite slab
• the strength of welds
• the decay of teeth
Early work in diffusion
• Thomas Graham (University of Glasgow)
– diffusion of gases (1828 ~ 1833); constant pressure
– The flux by diffusion is proportional to the
concentration difference of the salt

‘‘the quantities diffused appear to be closely in proportion . . . to the quantity of salt in the
diffusion solution’’ (Graham, 1850, p. 6).
• Adolf Eugen Fick (~1855)
– Diffusion can be described on the same mathematical basis as Fourier’s law for heat
conduction or Ohm’s law for electrical conduction
– One dimensional flux:

c1
J1  Aj1   AD
z
area across which diffusion occurs distance concentration
the flux per unit area diffusion coefficient

– Paralleled Fourier’s conservation equation

c1   2 c1 1 A c1  Fick’s second law:
 D 2  
t  z A z z  one-dimensional unsteady-state diffusion
Fick’s first law:

This is analogous to Newton’s law  yx   dvx

dy

This is analogous to Fourier’s law q x   dT

dx
q  T or j  Dc

These equations imply no convection (dilute solutions !).

Steady diffusion across a thin film
Example 2.1.1: Diffusion across a thin film Goal: concentration profile in the film, and the flux across it at steady state.

• On each side of the film is a well-mixed solution of one

solute, cl0 > cl1
• Mass balance in the layer z
Dividing this equation by the film’s volume, A∆z,
and rearranging,
Steady state

Take the limit as ∆z 0

Combining this equation with Fick’s law

,For constant D
This differential equation is subject to two boundary conditions:

Because this system is in steady state, the concentrations c10 and c1l are independent
of time.

Mathematical Solution:

The desired concentration profile and flux are now easily found. First, we integrate the above differential
equation twice

The constants a and b can be found from the boundary conditions.

so the concentration profile is (linear variation)

The flux is found by differentiating this profile:

 Derive the concentration profile and the flux for a single solute diffusing across
a thin membrane. The membrane is chemically different from the solutions.

Similar to the previous slide, a steady-state mass balance gives:

d 2 c1
0D 2
dz
B.C.
z = 0, c1 = HC10
z = l, c1 = HC1l
z
c1  HC10  H (C1l  C10 )
l

Different boundary conditions are used;

where H is a partition coefficient. H is a partition coefficient, the concentration in the membrane
This implies that equilibrium exists across the divided by that in the adjacent solution
membrane surface. Solute diffuses from the solution (Partition coefficient is an equilibrium property).
into the membrane.
The flux across a thin membrane can be found by combining the foregoing
concentration
profile with Fick’s law:

[DH] is called the permeability.

• The partition coefficient H is found to vary more widely than the diffusion coefficient
D, so differences in diffusion tend to be less important than the difference in
solubility.
Derive the concentration profile and the flux for a single solute
diffusing across a micro-porous layer.

Micro-porous layer

No longer one-dimensional

Effective diffusion coefficient is used

[DH ] [Deff H ]
j1  (C10  C1l ) j1  (C10  C1l )
l l
Homogeneous membrane Micro-porous layer

Deff = f (solute, solvent, local geometry)

Membrane diffusion with fast reaction
A solute is diffusing steadily across a thin membrane, it can rapidly and reversibly react with
other immobile solutes fixed with the membrane. Derive the solute’s flux.
A mass balance for reactant 1 gives:

rate of rate of diffusion rate of

Solute
accumulation
= diffusion into out of the layer consumption
the layer at z at z + z by reaction
s.s
0  Aj1 z  j1 z z  r Az
1 0
d
j1  r1
dz
A mass balance for (immobile) product 2 gives:

0  r1 Az 0  r1
d
0 j1
dz
The reaction has no effect.
Example: Diaphragm-cell diffusion
Goal: To measure the diffusion coefficient

• Two well-stirred volumes

separated by a thin porous
barrier or diaphragm.
Solvent • The diaphragm is often a
sintered glass frit/ a piece of
filter paper.
Solution of known
Conc.
• Calculate the diffusion
coefficient when the
Well-stirred solutions concentrations of the two
volumes as a function of time
are known.
Procedure:
Upper compartment = solvent, c01,upper
Lower compartment = solution, c 01,lower
After time t, measure new c1 at the upper and lower
compartment

Assumptions: Rapid attainment of steady state flux across the

diaphragm.

Note that this says the flux is steady even through the
concentrations are changing! Can we get away with that?
Assuming the flux across the diaphragm quickly reaches its steady-
state value, although the concentrations in the upper and lower
compartments are changing with time:

Pseudo steady-state for membrane diffusion

[DH ]
j1  (C1,lower  C1,upper )
l
H includes the fraction of the diaphragm’s area that is available for diffusion.

Overall mass balance on the adjacent compartments

dC1,lower
Vlower   Aj1
 1 
dt d
dt
C1,lower  C1,upper  Aj1 
 1


dC1,upper
  Aj1  Vlower Vupper 
Vupper
dt
A is the diaphragm’s area
  1 
d
dt
C1,lower  C1,upper  Aj1 

V
1

V 
 lower upper 
[DH ]
j1  (C1,lower  C1,upper )
l

 1 
d
dt

C1,lower  C1,upper  A
[DH ]
l

(C1,lower  C1,upper ) 
V
1

V 
 lower upper 
[H ]  1 1 
A 

l  Vlower Vupper 
@ t =0
d
C1,lower  C1,upper  D (C1,lower  C1,upper ) C1,lower  C1,upper  C1,lower
o
 C1,upper
o
dt

C1  0
C1,lower  C1,upper 
C 1,lower  C 0 1,upper 
*


C1  DC1* D   ln C1* 
d * 1
dt t
 Find the flux across a thin film in which diffusion varies sharply (i.e., the diffusion
coefficient is not a constant). Assume that below some critical concentration c1c,
diffusion is fast, but above this concentration it is suddenly much slower.

left d dc1
c10 l 0 j1 j1  D L
dz dz

DL
 j1dz  D L  dc1 c10  c1c 
zc c1c
c1c j1 
c1l 0 c 10 zc
zc
right 0   d j dc1
1 j1  D R
dz dz
large diffusion coefficient
small diffusion coefficient
DR
 j1dz  DR  dc1 c1c  c1l 
l c1l
j1 
zc c1c l  zc
DL c10  c1c  DR c1c  c1l 
The flux is the same across both films: j1 
l
In film 1: Large dc  smallD s
dz
zc c1c
dc 1 Ds
j1  D s   j1 dz   D s  dc 1 j1  (c 10  c 1c ) (1)
dz 0 c10 zc

In film 2: Small dc  large D 𝑙

dz
𝑙 c1𝑙
dc1 D𝑙
j1  D𝑙   j1 dz   D 𝑙  dc 1 j1  (c1c  c1𝑙) (2)
dz zc c1c 𝑙 z c

𝑙(c10 c1c )Ds 𝑙

(1) = (2)  zc  zc 
D s (c 10  c 1c )  D (c
𝑙 1c  c 1𝑙) 𝑙 (c 1c  c 1𝑙)
1 D
Ds(c10 c1c )

Ds(c10  c1c )  D (c
𝑙 1c  c 1𝑙)
The flux becomes then: j1 
𝑙
If
c c
c 1c  10 1𝑙 then D  Ds  D𝑙
2 2
 Skin diffusion
Skin behaves as if it consists of two layers, each of which has a different gas
permeability. Explain how these two layers can lead to the rashes observed.

p1+p2 Assuming that the gas pressure is in equilibrium

with the local concentration:
lA+lB
p1,gas concentration gas pressure
p1i p2,tissue
For layer A, p1  p1,gas 
z
lA
p1i  p1,gas 
p2,gas
z  lA
gas outside A B p1,tissue For layer B, p1  p1i  p1,tissue  p1i 
lB
the body

The flux through layer A equals that through layer B :

j1 
[DA H A ]
( p1,gas  p1i )  D A H A  p   DB H B  p
1,gas 1,tissue
lA  lA   lB 
p1i 
[DB H B ]  D A H A   DB H B 
 ( p1i  p1,tissue )   
lB  l A   lB 