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Lecture 1

Diffusion in dilute solutions


Mass transfer
Convection
Free convection and forced convection

Diffusion
diffusion is caused by random molecular motion that
leads to complete mixing.
in gases, diffusion progresses at a rate of about 10 cm/min;
in liquid, its rate is about 0.05 cm/min;
in solids, its rate may be only about 0.00001 cm/min

less sensitive to temperature than other phenomena

Diffusion
When it is the slowest step in the sequence, it
limits the overall rate of the process:

commercial distillations
rate of reactions using porous catalysts
speed with which the human intestine absorbs nutrients
the growth of microorganisms producing penicillin
rate of the corrosion of steel
the release of flavor from food

Dispersion (different from diffusion)


the dispersal of pollutants

Understand 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 Ficks law and a diffusion
coefficient
Engineering description: By a mass transfer coefficient

Models for diffusion


Mass transfer: define the flux
amount of gas removed
carbon dioxide flux
(time)(unit area )

Two models (from assumptions!)


Ficks law
carbon dioxide concentration difference

carbon dioxide flux D


capillary length

Mass transfer coefficient model


carbon dioxide flux k carbon dioxide concentration difference

Models
The choice between the mass transfer and diffusion
models is often a question of taste rather than
precision.
The diffusion model
more fundamental and is appropriate when concentrations
are measured or needed versus both position and time

The mass transfer model


simpler and more approximate and is especially useful
when only average concentrations are involved.

Diffusion in dilute solutions

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
hydrogen

air

stucco plug
glass tube
diffusion gas

water
Apparatus for liquids

Adolf Eugen Fick (~1855)


Diffusion can be described on the same mathematical basis as
Fouriers law for heat conduction or Ohms law for electrical
conduction
One dimensional flux:

J1 Aj1 AD
area across which diffusion occurs

c1
z
distance concentration

Paralleled
Fouriers
equationcoefficient
the flux
per unitconservation
area
diffusion

2 c1 1 A c1
c1

2
t
A z z
z

Ficks second law:


one-dimensional unsteady-state diffusion

Steady diffusion across a thin film


On each side of the film is a well-mixed solution
of one solute, c10 > c1l
Mass balance in the layer z

c10

Solute
accumulation

c1l

z
z

s.s.

rate of diffusion
out of the layer
at z + z

rate of
diffusion into
the layer at z

0 A j1 z j1

z z

0 A j1 z j1

z z

d 2 c1
0D 2
dz

Dividing A z

j1 z z j1 z
0
( z z ) z

z 0

d
0
j1
dz
c1
j1 D
z

d 2 c1
0D 2
dz

B.C.
z = 0, c1 = c10
z = l, c1 = c1l

z
c1 c10 (c1l c10 )
l

linear concentration
profile

c1
j1 D
z
j1

D
c10 c1l
l

Since the system is in s.s.,


the flux is a constant.

c10

c1l

z
z

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
0D 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.
This implies that equilibrium exists across the
membrane surface.
Solute diffuses from the solution into the
membrane.

c10

c10

c1l

c1l

H
10
1l

chemical potential: driving force

z
c1 HC10 H (C1l C10 )
l
c1
j1 D
z

[ DH ]
j1
(C10 C1l )
l
[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

[ Deff H ]

[ DH ]
j1
(C10 C1l )
l

j1

Homogeneous membrane

Micro-porous layer

(C10 C1l )

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 solutes flux.
A mass balance for reactant 1 gives:

rate of
diffusion into
the layer at z

0 A j1 z j1

r Az

Solute
accumulation

rate of diffusion
out of the layer
at z + z

rate of
consumption
by reaction

s.s
z z

d
0
j1 r1
dz

A mass balance for (immobile) product 2 gives:

0 r1 Az

0 r1

d
0
j1
dz
The reaction has no effect.

Diaphragm cell
Two well-stirred volumes separated by
a thin porous barrier or diaphragm.
The diaphragm is often a sintered glass
frit/ a piece of filter paper.
Calculate the diffusion coefficient
when the concentrations of the two
volumes as a function of time are
known.
Well-stirred solutions

Assuming the flux across the diaphragm quickly reaches its steadystate 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 diaphragms area that is available for diffusion.

Overall mass balance on the adjacent compartments


Vlower
Vupper

dC1,lower
dt
dC1,upper
dt

Aj1
Aj1

A is the diaphragms area

d
C1,lower C1,upper Aj1 1 1
dt
Vlower Vupper


d
C1,lower C1,upper Aj1 1 1
dt
Vlower Vupper

[ DH ]
j1
(C1,lower C1,upper )
l

d
[ DH ]
1
1
C1,lower C1,upper A
(C1,lower C1,upper )

V
dt
l
Vupper
lower

[ H ] 1
1
A

l Vlower Vupper

d
C1,lower C1,upper D (C1,lower C1,upper )
dt

C1,lower C1,upper
*
C1 0
C 1,lower C 01,upper

d *
C1 DC1*
dt

1
D ln C1*
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 c 1c,
diffusion is fast, but above this concentration it is suddenly much slower.

left

c10

zc

c1c

d
dc1
0
j1 j1 DL
dz
dz

c1l

zc

c1c

j1dz DL dc1
c10

right 0 d j
1

dz

large diffusion coefficient


small diffusion coefficient

zc

dc1
j1 DR
dz
c1l

j1dz DR dc1

The flux is the same across both films:

DL
c10 c1c
j1
zc

c1c

DR
c1c c1l
j1
l zc

DL c10 c1c DR c1c c1l


j1
l

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

p1,gas

lA+lB

p2,tissue

p1i

Assuming that the gas pressure is in equilibrium


with the local concentration:

concentration
For layer A,

z
p1 p1, gas p1i p1, gas
lA

For layer B,

z lA
p1,tissue p1i
p1 p1i
lB

p2,gas
gas outside
the body

A B

p1,tissue

gas pressure

The flux through layer A equals that through layer B :

[D H ]
j1 A A ( p1, gas p1i )
lA
[D H ]
B B ( p1i p1,tissue )
lB

p1i

DA H A
D H

p1, gas B B p1,tissue


lA
lB
DA H A DB H B

l A lB

Unsteady diffusion in a
semiinfinite slab - free diffusion
Any diffusion problem will behave as if the slab is
infinitely thick at short enough times.
At time zero, the concentration at z = 0 suddenly increases to c 10
Mass balance on the thin layer Az

c10

Solute
accumulation =

time

c1
position z

rate of
diffusion into
the layer at z

rate of diffusion
out of the layer
at z + z

Azc1 A j1 z j1
t

z z


Azc1 A j1 z j1
t

z z

c1
2 c1
D 2
t
z

Boundary conditions
c1 c1 at t 0, for all z

Dividing A z

j1 z z j1 z

c1
t
( z z ) z

z 0

c1

j1
t
z
c1
j1 D
z

c1
2 c1
D 2
t
z
Ficks second law

c1 c10

at t 0, z 0

c1 c1

at t 0, z

c1 c10
erf
c1 c10
j1 D

c1
z

j1 D

c1
D

e
z
t

j1

z 0

z
4 Dt

erf

z2
4 Dt

D
c10 c1
t

e s ds

c10 c1

Free diffusion with fast reaction


A solute is diffusing steadily across a semiinfinite slab, it can rapidly and reversibly
react with other immobile solutes fixed within the slab. Derive the solutes flux.
A mass balance for reactant 1 gives:
Solute
accumulation

Azc1 A j1 z j1
t
For a first-order reaction

Use

rate of diffusion
out of the layer
at z + z

rate of
diffusion into
the layer at z

D
to replace D
1 k

z z

r Az
1

rate of
generation
by reaction

c1
2 c1
D 2 r1
t
z

r1 kc1
c1
2 c1
D 2 kc1
t
z

c1
D 2 c1
The reaction has left the mathematical form of the answer

t
1

z
unchanged, but it has altered the diffusion coefficient.

If the same B.C.s are used:


Without reaction

With first-order fast reaction

c1
2 c1
D 2
t
z
c1 c10
erf
c1 c10

j1

z 0

c1
D 2 c1

t 1 k z 2

z
4 Dt

2
erf

s2

ds

D
c10 c1

c1 c10
erf
c1 c10

j1

z 0

z
D
4
t
1

erf

D
c10 c1
1 k t

e s ds

A sharp pulse of solute


The initial sharp concentration gradient relaxes by diffusion in the z
direction into the smooth curves. Calculate the shape of these curves.
Mass balance on the differential volume Az
Solute
accumulation
in Az

Position z

rate of
diffusion into
this volume

Azc1 Aj1 z Aj1


t

Dividing A z
z 0

c1

j1
t
z

rate of diffusion
out of this volume

z z

c1
j1 D
z

c1
2 c1
D 2
t
z

Boundary conditions
t 0, z , c1 0
t 0, z 0,

far from the pulse, the solute concentration is zero

c1
0
z

t 0, z 0, c1

at z = 0, the flux has the same magnitude in the positive


and negative directions

M
( z)
A
all the solute is initially located at z = 0
A: the cross-sectional area over which diffusion is occurring
M: the total amount of solute in the system
(z): the Dirac function (length)-1

M
c1 Adz A ( z ) Adz M

c1
2 c1
Apply Laplace Transform to solve
D 2
t
z

2 c1
c1
d 2 c1 ( s )
t s c1 ( s ) and z 2 dz 2

z and c1 are independent variables

c1
2 c1
D 2
t
z

Laplace transform

d 2 c1 ( s )
s c1 ( s ) D
dz 2

Second order linear O.D.E.

Dc1 s c1 0

s regards as constant

c1 Ae

s
z
D

Be

s
z
D

The boundary condition: t 0, z 0, c M ( z )


1
A

t 0, z , c1 0

Laplace transform

d c1
M 1

at z 0
dz
A 2D

c1 Ae

s
z
D

Be

A
c1
2D

c1 0

s
z
D

D
e
s

Laplace transform

c1 0

at z

at z

d c1
M 1

at z 0
dz
A 2D
s
z
D

inverse transform

c1

A e
4Dt

Gaussian curve

z2

4Dt

The steady dissolution of a spherical particle


The sphere is of a sparingly soluble material, so that the spheres size
does not change much. However, the material quickly dissolves in
the surrounding solvent, so that solutes concentration at the spheres
surface is saturated. The sphere is immersed in a very large fluid
volume, the concentration far from the sphere is zero. Find the
dissolution rate and the concentration profile around the sphere.

Mass balance on a spherical shell of thickness r


located at r from the sphere:
Solute
accumulation
within the shell

rate of
diffusion into
the shell

rate of diffusion
out of the shell

4r 2 rc1 4r 2 j1 r 4r 2 j1
t

s.s

r r

0 4r j1 r 4r j1
2

r r

Dividing 4r2r
r 0

1 d 2

0 2
r j1
r dr

Boundary conditions
r R0 , c1 c1 ( sat )
r , c1 0

c1
j1 D
r

D d 2 dc1
0 2 2 r
r dr
dr

R0
c1 c1 ( sat )
r
j1 D

Example:
The growth of fog droplets and the dissolution of drugs

c1
r

R0
j1 D 2 c1 ( sat )
r

The diffusion of a solute into the cylinder


The cylinder initially contains no solute. At time zero, it is suddenly
immersed in a well-stirred solution that is of such enormous volume
that its solute concentration is constant. The solute diffuses into the
cylinder symmetrically. Find the solutes concentration in this
cylinder as a function of time and location.
Mass balance on a cylindrical shell of thickness
r located at r from the central axis:
z
r

Solute
accumulation
within the shell

rate of
diffusion into
the shell

rate of diffusion
out of the shell

2rLrc1 2rLj1 r 2rLj1


t

r r


2rLrc1 2rLj1 r 2rLj1
t
Dividing 2rLr
r 0

1
c1
rj1
t
r r
j1 D

c1
r

c1 D c1

r
t
r r r

r r

Boundary conditions
t 0, all r , c1 0
t 0, r R0 , c1 c1 ( surface)
t 0, r 0,

c1
0
r

t 0, all r , c1 0

c1 D c1

r
t
r r r

t 0, r R0 , c1 c1 ( surface)
t 0, r 0,

c1
0
r

Dimensionless:

c1
1
c1 ( surface)

R0

Dt
2
R0

0, all , 1
0, 1, 0
0, 0,

0, all , 1
0, 1, 0
0, 0,

Assume: g f ( )

Using the method of Separation of variables

Please refer to my lecture note number 8 for the applied mathematics.

2
n

J
(

)
e
0 n

J
(

)
n 1
n 1
n

c1
1 2
c1 ( surface)
n 1

J 0 ( n r

R0

)e

D n 2t / R0 2

n J1 n r
R0

Diffusion across a thin, moving liquid film


The concentrations on both sides of this film are fixed by
electrochemical reactions, but the film itself is moving steadily.
Direction of diffusion
z

c10

c1l

Assumptions:
the liquid is dilute
the liquid is the only resistance to mass transfer
diffusion in the z direction
convection in the x direction

control volume

Mass balance on a control volume W x z :

moving liquid film

Solute
accumulation
in Wxz

c1Wxz j1Wx z j1Wx


t

rate of
diffusion in
the x direction

rate of
diffusion in
the z direction

z z

c v Wz
1 x

c1v xWz

x x


c1Wxz j1Wx z j1Wx
t
s.s.

z z

c v Wz
1 x

Dividing Wx z
x 0
z 0

c1v xWz

Neither c1 nor vx change with x

dj1
0
dz
j1 D

d 2 c1
0 D 2
dz

dc1
dz

B.C.
z 0, c1 c10

z l , c1 c1l

x x

z
c1 c10 (c1l c10 )
l
j1

D
c10 c1l
l
The flow has no effect!

Diffusion into a falling film


A thin liquid film flows slowly and without ripples down a flat
surface. One side of this film wets the surface; the other side is in
contact with a gas, which is sparingly soluble in the liquid. Find how
much gas dissolve in the liquid.
z

solute gas
x

control volume

Assumptions:
the liquid is dilute
the contact between gas and liquid is short
diffusion in the z direction
convection in the x direction

Mass balance on a control volume W x z :


Liquid with dissolved
solute gas

Solute
accumulation
in Wxz

c1Wxz j1Wx z j1Wx


t

rate of
diffusion in
the x direction

rate of
diffusion in
the z direction

z z

c v Wz
1 x

c1v xWz

x x


c1Wxz j1Wx z j1Wx
t

z z

c v Wz
1 x

c1v xWz

x x

Dividing Wx z
x 0
z 0

s.s.

j1
0
c1v x
z x
vx ~ constant

j1 D

dc1
dz

c1
2 c1
D 2
x / vx
z

B.C.

x 0, all z , c1 0
x 0, z 0, c1 c1 ( sat )
x 0, z l , c1 0

c1
1 erf
c1 ( sat )
j1

z 0

z
4 Dx / v x

vx
D c1 ( sat )
x

What we have done are:


1. We write a mass balance as a differential equation
2. Combine this with Ficks law
3. Integrate this to find the desired result

D
j1 c1
l

For thin film

D
j1
c1 For thick slab
t
Fourier Number
2

(length)
( D)(time)

Much larger than unity . Assume a semiinfinite slab


Much less than unity ..Assume a steady state or an equilibrium
Approximately unity ... Used to estimate the process

Example:
Hydrogen has penetrated about 0.1 cm into nickel, D = 10-8 cm2/sec,
estimate the operation time of the process.
2

(length)
1
( D)(time)

(10 1 cm) 2
1
8
2
(10 cm / sec)(time)
Approximately 10 days.