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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
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
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
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
air
stucco plug
glass tube
diffusion gas
water
Apparatus for liquids
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
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
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
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
[ Deff H ]
[ DH ]
j1
(C10 C1l )
l
j1
Homogeneous membrane
Micro-porous layer
(C10 C1l )
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
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.
dC1,lower
dt
dC1,upper
dt
Aj1
Aj1
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
zc
dc1
j1 DR
dz
c1l
j1dz DR dc1
DL
c10 c1c
j1
zc
c1c
DR
c1c c1l
j1
l zc
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
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
[D H ]
j1 A A ( p1, gas p1i )
lA
[D H ]
B B ( p1i p1,tissue )
lB
p1i
DA H A
D H
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
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.
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
Position z
rate of
diffusion into
this volume
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,
c1
0
z
t 0, z 0, c1
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
c1
2 c1
D 2
t
z
Laplace transform
d 2 c1 ( s )
s c1 ( s ) D
dz 2
Dc1 s c1 0
s regards as constant
c1 Ae
s
z
D
Be
s
z
D
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
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
Solute
accumulation
within the shell
rate of
diffusion into
the shell
rate of diffusion
out of the shell
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 ( )
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
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
Solute
accumulation
in Wxz
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
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!
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
Solute
accumulation
in Wxz
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
D
j1 c1
l
D
j1
c1 For thick slab
t
Fourier Number
2
(length)
( D)(time)
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.