Mass Transfer
Modes of mass transfer
1. Diffusion
1a. Molecular diffusion
1b. Knudsen diffusion (Gas)
2. Convection
Diffusion is more complicated than viscous flow
or heat conduction because we have to deal
with mixtures (more than one component)
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Definitions of C, u, J
1. Concentrations
Solution refers to one phase either
gaseous, liquid or solid mixtures
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2. Velocities and average velocities
a. Various species move at different velocities.
b. Let vk be the velocity of the species k relative to the stationary
coordinate.
c. The local mass average velocity is defined as:
(the average of all the velocities of molecules of species k within
a small volume).
Note that : v is the local mass rate through a unit cross section placed
perpendicular to the velocity v
This mass average velocity is the local velocity one would measured by a
pitot tube
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d. The local molar average velocity is defined as:
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3. Diffusion velocities
In flow systems, we are interested in the velocity of
species j with respect to v local mass average velocity
or v* local molar average velocity , rather than with
respect to the stationary coordinates.
There are two diffusion velocities:
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There are two diffusion velocities. In applications where we
deal with molar flow, the diffusion velocities with respect to v*
will be used.
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4. Mass and molar fluxes relative to stationary coordinates
a. Mass flux
which is the mass of species j transferred per unit time and per unit
area perpendicular to the velocity vj.
b. Molar flux
which is the moles of species j transferred per unit time and per unit
area perpendicular to the velocity vj.
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5. Diffusive mass and molar fluxes
a. Mass fluxes relative to the local mass average velocity
b. Molar fluxes relative to the local molar average velocity
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6. Properties of diffusive fluxes
This equation means that
within the movement of the
bulk fluid mixture, the sum
of all the diffusive fluxes
must be zero so that the
pressure
is
maintained
constant.
For a binary mixture, we have:
J1 = - J2
Two species move in the opposite
direction (relative to the
movement of the mixture).
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7. Diffusive molar fluxes(J) versus molar fluxes (N)
This equation simply states that the diffusive molar flux of species j
is equal to the molar flux minus its contribution in the total flux.
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Ficks law of diffusion for binary mixtures
Here, we first study the diffusion law for binary mixtures: The Ficks law
For multicomponent mixtures, the correct law is the Stefan-Maxwells law.
This is more complicated, and will be dealt with much later.
1. The Ficks law:
The basic equation for Ficks law for an isobaric and isothermal system is:
which is the diffusive molar flux along the z direction.
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These two equations are not linearly
independent.
Thus, only ONE is sufficient.
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3. Diffusion coefficient
c. Temperature and pressure dependence
For gases at low density, D increases with
T and decreases with pressure.
For liquids and solids, D increases with
temperature.
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Procedures for binary mixtures
Similar to momentum and energy transfers.
Steps 1 to 4: involve draw a physical diagram and a thin shell with
surfaces perpendicular to transport directions.
Step 5: Set up mass balance equation of the thin shell
Taking the shell as thin as possible will yield a first order differential
equation in terms of molar flux.
Step 6: Apply the Ficks law
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Depending on the physical system, N2 must be determined based
on the physical ground.
Step 7: Impose physical constraints
Step 8: Solve for concentration distribution
Step 9: Solve for desired quantity, such as average concentration,
molar fluxes.
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Boundary conditions
Generally, there are five boundary conditions:
B.C. of the first kind:
Concentration is specified at the boundary
B.C. of the second kind:
Molar flux is specified at the boundary
B.C. of the third kind:
Molar flux into the medium is the same as the flux
through a stagnant film surrounding the medium
B.C. of the fourth kind:
Concentrations and fluxes are continuous across
the interface of two adjoining media.
B.C. of the fifth kind:
Molar flux is equal to the surface reaction
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Problem: Diffusion in a Stefan tube
Physical system
1. Liquid 1 in the tube
2. Gas 2 flowing across the mouth of the tube
3. Gas 2 is nonsoluble in liquid 1
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which states that the molar flux is
constant along the tube.
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we solve for N1 in terms of the concentration gradient.
Substitute this into the mass balance equation:
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For constant total pressure and constant diffusion coefficient, we
have:
which is a second-order differential equation in terms of mole fraction.
Step 7: Physical constraint
The two boundary conditions are:
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Step 8: Concentration distribution
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Thus, the concentration profile is:
Step 9: Molar flux
The quantity of interest is the molar flux from the liquid surface
(evaporation rate):
Usually molar flux is evaluated at the liquid surface, BUT in this
problem it can be evaluated anywhere as the molar flux is
constant along the tube.
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During the integration for the concentration profile, we see that:
Thus, the evaporation rate is:
If the gas 2 is sweeping past the mouth fast enough, the
concentration of the species1, x1,L, at the mouth will be effectively
zero; hence the evaporation rate is:
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Drop in liquid level
Due to evaporation, the liquid level will drop, and to determine this
drop in level versus time, we have to do the mass balance equation
around the liquid.
the evaporation rate = molar flux * Mol Wt *CS Area
The initial condition is: t=0;
on Integration
z1 = z10
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Example:
Species 1: Carbon tetrachloride
Species 2: Air
R = 82.05 cm3-atm/mole/K
Operating conditions
P = 760 mmHg
T = 273 K
Species characteristics
p10 = 33 mmHg
M1 = 154 g/mole
L = 1.59 g/cc
D12 = 0.0636 cm2/sec
Tube height and initial liquid level
z2 = 40 cm
z10 = 25 cm
Answer: t* = 651 days
Reasons for this extremely long time
required to empty the tube:
a. low vapor pressure
b. very long diffusion path in the tube
c. very low diffusion coefficient
Conclusion:
Diffusion is a very slow process.
Mixing is done to speed up this process.
One way of doing is to reduce the diffusion
path length.
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Dissolution of a sphere
Sparingly soluble sphere in a surrounding fluid of infinite extent.
Shell mass balance
The mass balance equation around the thin
shell at r and having a thickness of r is:
The object (species 1) dissolves
in surrounding fluid 2 with the
solubility of C10.
Divide the equation by 4r, and take the
limit of the result when r approaches zero,
we get
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Ficks law equation:
can be taken as zero as the species 1 (object) is only
sparingly soluble in liquid 2
Thus, the mass balance equation will become:
dC1
d
r
D
2 12
=0
dr
dr
k1
dC1
=
;
2
dr
D
r
12
Physical constraints
r = R (surface of object);
r ;
C1 = 0
C1 = C10
Concentration distribution
Dissolution rate
C1 =
C1 = C10
N1 = D12
= D12
R
r
dC1
dr
k1
+ k 2 BC 2, k 2 = 0
D12 r
C1 = C10
R
r
;Q BC1, k1 = C10 RD12
C10
R
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C10
N1 = D12
R
To increase the dissolution rate:
1. smaller object
2. larger solubility
3. larger diffusivity
If we define the mass transfer coefficient as:
C10
D12
= kmC10
R
k D
2 = m ; Schmidt
D12
Number
Schmidt number, which is equal to 2 for
stagnant environment
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Home Work: Diffusion with heterogeneous reaction
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Diffusion with homogeneous chemical reaction of a solid sphere in a liquid
A solid sphere (of radius R and density r) made of substance A (of molecular
weight M) is suspended in a liquid B. Solid A undergoes a first-order
homogeneous chemical reaction with rate constant k1''' being slightly soluble in
liquid B. Let cA0 be the molar solubility of A in B, and DAB be the diffusivity of A
in B.
Figure. Diffusion with chemical reaction
of sphere in liquid.
a) Establish the concentration profile for A at steady state (i.e., when
the mass diffusion is in exact balance with the chemical reaction).
b) Using a quasi-steady-state approach, derive an expression for the
time t required for the sphere radius to decrease from an initial radius
R0 to R.
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ASSIGNMENT III
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