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
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:
c
J1 Aj1 AD 1
z
area across which diffusion occurs distance concentration
the flux per unit area diffusion coefficient
z
c1 HC10 H (C1l C10 ) H H
l
Different boundary conditions are used;
where H is a partition coefficient. 10
This implies that equilibrium exists across the
membrane surface.
Solute diffuses from the solution into the 1l
membrane.
Micro-porous layer
No longer one-dimensional
[ DH ] [ Deff H ]
j1 (C10 C1l ) j1 (C10 C1l )
l l
Homogeneous membrane Micro-porous layer
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.
Well-stirred solutions
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:
[ DH ]
j1 (C1,lower C1,upper )
l
H includes the fraction of the diaphragms area that is available for diffusion.
1
d
C1,lower C1,upper A [ DH ]
(C1,lower C1,upper )
1
dt l Vlower Vupper
[ H ] 1 1
A
l Vlower Vupper
d
C1,lower C1,upper D (C1,lower C1,upper )
dt
C
*
C 1,lower C1,upper
1
C 0
1,lower C 01,upper
d *
dt
C1 DC1*
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 c1c,
diffusion is fast, but above this concentration it is suddenly much slower.
left d dc1
c10 l 0 j1 j1 DL
dz dz
DL
c10 c1c
zc c1c
c1c c1l
0
j1dz DL dc1
c10
j1
zc
zc
right 0 d j j1 DR
dc1
1
dz dz
large diffusion coefficient
small diffusion coefficient DR
c1c c1l
l c1l
zc
j1dz DR dc1
c1c
j1
l zc
DL c10 c1c DR c1c c1l
The flux is the same across both films: 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.
c1 Azc1 A j1 z j1 z z
t
position z
c1 2 c1
Azc1 A j1 z j1 z z t
D 2
z
t
Boundary conditions
Dividing A z
c1 c1 at t 0, for all z
c1 c10 at t 0, z 0
j1 z z j1 z
c1
c1 c1 at t 0, z
t ( z z ) z z
z 0 c1 c10 4 Dt
erf
c1 c1 c10 erf
2
e s ds
2
j1 0
t z j1 D
c1
z
c1
j1 D z2
z c1
j1 D
D
e 4 Dt
c10 c1
z t
c1 2 c1
D 2
t z
j1 z 0
D
c10 c1
Ficks second law t
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:
Azc1 A j1 z j1 z z r Az c1 2c1
D 2 r1
t
1
t z
c1 2 c1 c1 D 2c1
D 2
t z t 1 k z 2
z
z
D
c1 c10 c1 c10 4 t
erf 4 Dt
erf 1 k
c1 c10 2 c1 c10
erf e s2
ds 2
erf e s ds
2
0
j1
D
c10 c1 j1
D
c10 c1
z 0
t
z 0
1 k t
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.
Solute rate of
rate of diffusion
accumulation = diffusion into
out of this volume
in Az this volume
z
Position z
Azc1 Aj1 z Aj1 z z
t
Dividing A z
z 0 c1
j1 D
c1 z c1 2 c1
j1 D 2
t z t z
Boundary conditions
t 0, z , c1 0 far from the pulse, the solute concentration is zero
c1
t 0, z 0, 0 at z = 0, the flux has the same magnitude in the positive
z and negative directions
M
t 0, z 0, c1 ( z)
A
M
c1 Adz A ( z ) Adz M
c1 2 c1
Apply Laplace Transform to solve D 2
t z
c1 2c1 d 2 c1 ( s)
s c1 ( s ) and 2
t 2
z dz
z and c1 are independent variables
c1 2 c1 d 2 c1 ( s)
D 2 Laplace transform
sc1 ( s) D
t z dz 2
s s
z z
Dc1 sc1 0 s regards as constant c1 Ae D
Be D
The boundary condition: t 0, z 0, c M ( z )
1
A t 0, z , c1 0
Laplace transform Laplace transform
d c1 M 1 c1 0 at z
at z 0
dz A 2D
s s c1 0 at z
z z
c1 Ae D
Be D
d c1 M 1
at z 0
dz A 2D
M
s inverse transform M z2
A D z
c1 e D
c1 A e 4Dt
2D s 4Dt
Gaussian curve
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.
t
4r 2 rc1 4r 2 j1 r 4r 2 j1 r r
s.s
0 4r j1 r 4r j1
2 2
r r Boundary conditions
Dividing 4r2r r R0 , c1 c1 ( sat )
r 0
r , c1 0
1 d 2
0 2
r dr
r j1
c1
j1 D
r
D d 2 dc1 R0
0 2 2 r c1 c1 ( sat )
r dr dr r
c1
j1 D
r
Example: R0
j1 D 2 c1 ( sat )
The growth of fog droplets and the dissolution of drugs 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.
z Solute rate of
rate of diffusion
accumulation = diffusion into
out of the shell
r within the shell the shell
2rLrc1 2rLj1 r 2rLj1 r r
t
2rLrc1 2rLj1 r 2rLj1 r r
t
Dividing 2rLr Boundary conditions
r 0
t 0, all r , c1 0
1
c1 rj1
t r r t 0, r R0 , c1 c1 ( surface)
c1
j1 D
r c1
t 0, r 0, 0
r
c1 D c1
r
t r r r
c1 D c1 t 0, all r , c1 0
r
t r r r
t 0, r R0 , c1 c1 ( surface)
c1
t 0, r 0, 0
r
Dimensionless:
c1 r Dt
1 2
c1 ( surface) R0 R0
1 0, all , 1
0, 1, 0
0, 0, 0
1 0, all , 1
0, 1, 0
0, 0, 0
n 1 n J1 ( n )
D n 2t / R0 2
J 0 ( n r )e
c1 R0
1 2
c1 ( surface) n 1 n J1 n r R
0
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 Assumptions:
the liquid is dilute
z the liquid is the only resistance to mass transfer
diffusion in the z direction
x convection in the x direction
c10 c1l control volume
dj1
0
dz
dc1
j1 D
dz
d 2 c1 z
0 D 2 c1 c10 (c1l c10 )
dz B.C. l
z 0, c1 c10
j1
D
c10 c1l
l
z l , c1 c1l
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.
s.s. Dividing Wx z
x 0
z 0
j1
0 c1v x
z x
dc1
vx ~ constant j1 D
dz
c1 2c1 c1 z
D 2 1 erf
x / vx z c1 ( sat ) 4 Dx / vx
B.C.
x 0, all z , c1 0 vx
j1 z 0 D c1 ( sat )
x 0, z 0, c1 c1 ( sat ) x
x 0, z l , c1 0
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 For thin film
l
D
j1 c1 For thick slab
t
Fourier Number
2 Much larger than unity . Assume a semiinfinite slab
(length) Much less than unity ..Assume a steady state or an equilibrium
( D)(time) 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 (101 cm) 2
8
1
( D)(time) 2
(10 cm / sec)(time)
Approximately 10 days.