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∑ρ
total mass
k
k =1
Mole fraction
Cj Cj mole of j
xj = = n
=
∑C
C total moles
k
k =1
Velocities and Average Velocities (1)
Different components move at different velocities
2 v2
1
v1
Let vj be the velocity of the component j, relative to the fixed frame of
coordinate. Thus the mass flux is (mass rate per unit cross-sectional area
perpendicular to the flow)
n
∑ρ v
k =1
k k
∑C v
k =1
k k
Velocities and Average Velocities (2)
Different components move at different velocities
2 v2
1
v1
n ∑ ρk vk ∑ ρk vk
ρk
ρv = ∑
n n
ρk v k v= nk =1
= k =1
= ∑ vk = ∑ ω k vk
ρ k =1 ρ
k =1 ∑ k
k =1
ρ k =1
Velocities and Average Velocities (3)
Different components move at different velocities
2 v2
1
v1
k =1
Diffusion Velocities (1)
The velocity relative to the fixed frame of coordinate is
sufficient to calculate the flux
But in flow systems, it is extremely useful to know the diffusion rate
of different components relative to the flow of the bulk solution
1
V
1
V
Mass Fluxes and Molar Fluxes
relative to the Fixed Frame (1)
Mass Fluxes
The mass flux of the component j is the product of the mass
concentration and the velocity of that component
⎛ mass of species j⎞ ⎛ dis tan ce ⎞
n j = ρ jv j = ⎜ ⎟ ×⎜ ⎟
⎝ volume ⎠ ⎝ time ⎠
which is the mass of the component j transported per unit time and
per unit cross sectional area perpendicular to the velocity vj
Mass Fluxes and Molar Fluxes
relative to the Fixed Frame (2)
Molar Fluxes
The molar flux of the component j is the product of the molar
concentration and the velocity of that component
⎛ mole of species j ⎞ ⎛ dis tan ce ⎞
N j = C jv j = ⎜ ⎟ ×⎜ ⎟
⎝ volume ⎠ ⎝ time ⎠
(
jj = ρ j v j − v )
which is the mass transferred per unit time per unit area, relative to
the bulk flow
Diffusion Mass and Molar Fluxes (2)
The diffusion molar flux is defined the flux relative to the
bulk motion of the solution
(
J j = C j v j − v* )
which is the moles transferred per unit time per unit area, relative to
the bulk flow
Properties of Diffusion Fluxes (1)
The diffusion fluxes satisfy the following equation
n n
∑j
k =1
k = 0; ∑J
k =1
k =0
2
For example, for a system of two components ∑J
k =1
k =0
which simply states that the diffusion flux of component 1 (to the
right, say) MUST be the same to the diffusion of component 2 (to the
left).
If this is NOT satisfied, what would be the consequence?
Properties of Diffusion Fluxes (2)
The diffusion fluxes satisfy the following equation
n n
∑j
k =1
k = 0; ∑J
k =1
k =0
Proof:
By definition n n n
∑ C (v ) ∑J = ∑C vk − v ∑C
n n *
∑J
k =1
k =
k =1
k k − v*
k =1
k
k =1
k
k =1
k
n n n n ∑C k vk
∑J
k =1
k = ∑C
k =1
k v k − v *C ∑J
k =1
k = ∑C
k =1
k vk − k =1
C
C
∑C k vk n
v = * k =1
C
∑J
k =1
k =0
Diffusion Flux vs Flux (1)
Recall the definitions of molar flux and molar diffusion flux
N j = C jv j J j = C j (v j − v *)
(
J k = C k v k − v* )
= Ckvk − Ckv * = Ckvk − Ck
j =1
n
Jk = Nk − xk ∑ N j
n
Ck
Jk = Ckvk −
C
∑C v
j =1
j j
j= 1
Diffusion Flux vs Flux (3)
The relationship between the molar flux and the molar diffusive flux is
n
Jk = Nk − xk ∑ N j
j= 1
This equation simply states that the diffusive flux of the component k is
equal to the flux of that component minus the fraction of that component in
the bulk flow
Diffusion Flux vs Flux (4)
Similarly, the relationship between the mass flux and the mass diffusive flux
is
n
jk = n k − ω k ∑ n j
j= 1
This equation again states that the diffusive flux of the component k is equal
to the flux of that component minus the fraction of that component in the
bulk flow
Fick’s law of Diffusion for Binary
Mixtures (1)
The basic law for diffusion study is the widely known Fick’s
law.
It is only applicable for BINARY mixture
For mixtures of three or more components, the proper law is the
Maxwell-Stefan law
The Fick’s law for the first component is
dx
J 1 = − cD 12 1
dz
which is only correct for isobaric and isothermal system.
This equation states that if there is a gradient in the mole fraction of
the component 1, the molar diffusive flux is calculated as above
The coefficient D12 is called the binary diffusivity
Fick’s law of Diffusion for Binary
Mixtures (2)
Similarly, we can write the same equation for the second component by
simply interchanging the subscripts 1 and 2
dx 1 dx 2
J 1 = − cD 12 J 2 = − cD 21
dz dz
But we know that the molar diffusive fluxes satisfy the following equation
J1 + J 2 = 0
Thus adding the two molar diffusive fluxes, we have
dx1 dx
J1 + J 2 = −cD12 − cD 21 2 = 0
dz dz
But x 1 + x 2 = 1
dx1 dx
The above equation will become J1 + J 2 = −cD12 + cD 21 1 = 0
dz dz
J1 + J 2 = −c(D12 − D 21 ) (D12 − D 21 ) = 0
dx1
=0
dz
Fick’s law of Diffusion for Binary
Mixtures (3)
Thus the diffusivity (diffusion coefficient) D12 is equal to the diffusivity D21
dx 2
J 2 = −cD 21
dz
are not independent. So only one is used. Either one will do.
J 1 = − cD 12 ∇ x 1
Fick’s law of Diffusion for Binary
Mixtures (4)
So the Fick’s law gives us the molar diffusive flux. What we need for mass
transfer calculation is the molar flux relative to the fixed frame of
coordinates
dx1
J 1 = − cD12
dz
Here is the place where we need the relationship between the molar
diffusive flux and the molar flux. This relationship is
n
J k = Nk − xk ∑ N j
j=1
which for binary mixtures, it is
N 1 = J 1 + x1 ( N 1 + N 2 )
2
J1 = N1 − x1 ∑ N j
j=1
Fick’s law of Diffusion for Binary
Mixtures (5)
So the equation for the molar flux is
dx1
J 1 = − cD12
dz
N 1 = J 1 + x1 ( N 1 + N 2 )
dx 1
N 1 = − cD12 + x1 ( N 1 + N 2 )
dz
This is the equation for the molar flux for the component 1. You can also
easily write an equation for the component 2 by interchanging the subscripts
1 and 2
dx 2
N 2 = − cD 21 + x 2 (N 2 + N1 )
dz
But only one of them is independent!
Fick’s law of Diffusion for Binary
Mixtures (6)
Summary
dx1
J 1 = − cD12
dz
dx 1
N 1 = − cD12 + x1 ( N 1 + N 2 )
dz
The above equation involves two unknown variables:
The molar flux of component 1, N1
The molar flux of component 2, N2
State P T
Pressure and Temperature
Gas decrease increase
Dependence
Liquid - increase
Solid - increase
Stefan-Maxwell’s law for mixtures
A bit excursion into the Stefan-Maxwell law.
The equation for mixtures of n components is
n
− c ∇x i = ∑
(x N
j i − xi N j )
j=1 D ij
for i = 1, 2, …, (n-1). Only (n-1) equations are independent as the n-th
equation can be derived from the other equations
− c ∇x i = ∑
n
(x J
j i − xi J j )
j=1 D ij
Take the limit of the mass balance equation as the shell shrinks to
zero. This will lead to a first-order differential equation with respect
to flux
Apply the Fick’s law, and we will get a second-order differential
equation in terms of concentration
First Principles for Binary Mixtures (2)
The procedure (continued)
Impose the constraints on the system (boundary conditions)
Solve for the concentration distribution
Knowing the concentration distribution, derive the average
concentration, molar fluxes, etc.
Boundary Conditions
There are five boundary conditions that you will regularly
encounter in mass transfer
BC of the first kind:
Concentration is specified at the boundary
BC of the second kind:
Molar flux is specified at the boundary
BC of the third kind:
Molar flux into a medium is equal to the molar flux through the stagnant
film surrounding the medium
BC of the fourth kind:
Concentrations and fluxes are continuous across the interface
BC of the fifth kind:
Molar flux to a surface is equal to the chemical reaction occurring on
that surface
What is next?
That is all about mass transfer!
What come next are simple examples to illustrate the mass transfer
principles.
Example 1: Diffusion in a Stefan tube
Example 2: Dissolution of a spherical objects
Example 3: Diffusion and heterogeneous reaction at surface
Example 4: Diffusion and homogeneous reaction
Example 5: Diffusion into a falling film
Example 6: Gas absorption in a rising bubble
Example 7: Diffusion and reaction in a porous catalyst
Example 8: Transient diffusion through a polymer film
Example 9: Transient diffusion in a finite reservoir
Diffusion in a Stefan tube (1)
Stefan tube is simply a test tube with
liquid in it.
Physical system:
Liquid 1 is in the tube
Gas 2 is flowing across the tube mouth
Gas 2 is non-soluble in liquid 1
Diffusion in a Stefan tube (2)
Shell balance
⎛ Rate of ⎞ ⎛ Rate of ⎞ ⎛ Rate of mass⎞
⎜ ⎟ −⎜ ⎟ +⎜ ⎟ = ( Accummulation)
⎝ mass in ⎠ ⎝ mass out⎠ ⎝ production ⎠
S⋅ N1 z − S ⋅ N1 z + ∆z +0 = 0
S ∆z
Taking the shell as thin as possible
dN 1
− =0
dz
Which simply state that the evaporation flux of the component 1 is
constant along the tube
Diffusion in a Stefan tube (3)
So the shell balance equation is
dN 1
− =0
dz
Apply the Fick’s law for binary system
dx 1
N 1 = − cD 12 + x1(N 1 + N 2 )
dz
Since the gas 2 is insoluble in liquid 1, the molar flux of component 2
(with respect to a person standing outside the tube) is simply ZERO. So
the Fick’s law is reduced to:
cD 12 dx 1
+ x 1 (N 1 )
dx 1 N1 = −
N 1 = − cD 12
dz 1 − x 1 dz
Diffusion in a Stefan tube (4)
The mass balance equation is
dN 1
− =0
dz
The Fick’s law
cD 12 dx 1
N1 = −
1 − x 1 dz
So the mass balance equation in terms of concentration is
d ⎛ cD 12 dx 1 ⎞ d ⎛ 1 dx 1 ⎞
⎜ ⎟=0 cD 12 ⎜⎜ ⎟⎟ = 0
dz ⎝ 1 − x 1 dz ⎠ dz ⎝ 1 − x 1 dz ⎠
For constant P and D12
Diffusion in a Stefan tube (5)
The mass balance equation in terms of
concentration is a second-order differential
equation
d ⎛ 1 dx 1 ⎞
cD 12 ⎜⎜ ⎟⎟ = 0 z2
dz ⎝ 1 − x 1 dz ⎠
Physical constraints (Boundary conditions)
p10
z = z1 ; x 1 = x 1, 0 = z1
P
z = z2 ; x 1 = x 1, L
0
Diffusion in a Stefan tube (6)
Solution procedure
d ⎛ 1 dx 1 ⎞
cD 12 ⎜⎜ ⎟⎟ = 0 z2
dz ⎝ 1 − x 1 dz ⎠
Integrate it once
cD 12 dx 1
= K 1 ( cons tan t ) z1
1 − x 1 dz
Integrate it one more time
⎛ 1 ⎞ 0
cD 12 ln ⎜ ⎟ = K1z + K 2
⎝ 1 − x1 ⎠
which involves two constants of integration
Did you note that K1 is simply the negative
of the molar flux N1?
Diffusion in a Stefan tube (7)
Solution
⎛ 1 ⎞ z2
cD 12 ln ⎜ ⎟ = K1z + K 2
⎝ 1 − x1 ⎠
z − z1 ⎛⎜ 1 − x1,L ⎞⎟
0
ln (1 − x1 ) − ln (1 − x1, 0 ) = ln⎜
z 2 − z1 ⎝ 1 − x1, 0 ⎟⎠
Now taking differentiation:
dx1 dz ⎛ 1 − x1,L ⎞ 1 dx1 1 ⎛ 1 − x1,L ⎞
− = ⎜
ln⎜ ⎟ − = ln ⎜ ⎟
1 − x1 z 2 − z1 ⎝ 1 − x1, 0 ⎟⎠ 1 − x1 dz z 2 − z1 ⎜⎝ 1 − x1, 0 ⎟⎠
Diffusion in a Stefan tube (11)
So we have
1 dx1 1 ⎛ 1 − x1,L ⎞
− = ln⎜⎜ ⎟ z2
1 − x1 dz z 2 − z1 ⎝ 1 − x1, 0 ⎟⎠
N1 =
( P / RT ) D 12 ln ⎛ 1 ⎞
⎜ ⎟
z 2 − z1 ⎝ 1 − p i0 / P ⎠
Diffusion in a Stefan tube (14)
Given the flux of species 1 as
N1 =
( P / RT ) D 12 ln ⎛ 1 ⎞ z2
⎜ ⎟
z 2 − z1 ⎝ 1 − p i0 / P ⎠
N1 + N2 =
( P / RT ) D 12 ln ⎛ 1 ⎞ z1
⎜ ⎟
z 2 − z1 ⎝ 1 − p 0
i / P ⎠
0
The flux of the component 2 is
+ x 2 (N 1 + N 2 ) = 0
dx 2
N 2 = − cD 12
dz
Diffusion in a Stefan tube (15)
Because of the evaporation, the liquid level
will drop with time
z2
=
( P / RT ) D 12 ⎛ 1 ⎞
N1 ln ⎜ ⎟
z 2 − z1 ⎝ 1 − p 0
i / P ⎠
The solution is
The time taken to empty the liquid is:
[ z 2 − z 1 ( t ) ]2 − ( z 2 − z 10 ) 2 =
t* =
z 22 − (z 2 − z 10 )
2
⎡ M 1 ( P / RT ) D 12 ⎛ 1 ⎞⎤ ⎡ M 1 (P / RT )D 12 ⎛ 1 ⎞⎤
ln ⎜ ⎟ ⎥t ⎢2 ⎜
ln ⎜ ⎟⎥
⎢2 ρL ⎟
⎝ 1 − p 1 / P ⎠ ⎦⎥
0
⎣ ρ L ⎝ 1 − p 0
1 / P ⎠⎦ ⎣⎢
Diffusion in a Stefan tube (17)
The time taken to empty the liquid is: z2
z 22 − (z 2 − z 10 )
2
t = *
⎡ M 1 (P / RT )D 12 ⎛ 1 ⎞⎤
⎢ ⎜ ⎟
2
ρ
ln ⎜ 1 − p 0 / P ⎟⎥
⎢⎣ L ⎝ 1 ⎠ ⎥⎦
z1
Example:
Carbon tetrachloride (1) in air (2) in a Stefan
tube of length 40 cm and the initial level of 0
the liquid is 25 cm.
The time taken to empty the liquid is 651
days!!
2R
r
Dissolution of a Sphere (2)
Physical system: Sparingly soluble sphere in a surrounding
fluid of infinite extent
The shell balance
( 4πr 2
N1 ) − ( 4πr
r
2
N1 ) r + ∆r
+0= 0
4 π ∆r
( r2 N1 ) ( − r2 N1 )
lim
∆r → 0
r
∆r
r + ∆r
=−
d 2
dr
(
r N1 = 0 )
r
Dissolution of a Sphere (3)
The shell balance −
dr
(
d 2
)
r N1 = 0
dx 1
The Fick’s law N 1 = − cD 12 + x1 (N 1 + N 2 )
dr
The second term is the contribution of the species 1 in the bulk flow.
Since the object is only sparingly soluble, x1 is expected very small.
Therefore we can ignore the bulk flow contribution in the Fick’s law
equation
dx
N1 ≈ −cD12 1
dr
N1 r= R
= k m ( C 10 − 0)
Comparing this equation with the dissolution rate obtained from the first
principles
D12 C10
N1 r = R =
R
You will get k m (2 R )
=2
D 12
It, therefore, comes as no surprise that some correlations for heat and mass
transfer take the following form:
Nu = 2 + 1.1 Re 0.6 Pr1/ 3 C pµ µ
Pr = ; Sc =
Sh = 2 + 1.1 Re 0.6 Sc1/ 3 k ρD12
Diffusion with Heterogeneous
Reaction (1)
Physical system:
Chemical reaction occurs on a catalytic surface
Catalytic surface is surrounded by a thin stagnant film
Diffusion occurs in the stagnant film
Isothermal conditions
Reaction is n A → A n
A
An
Diffusion with Heterogeneous n A → An
Reaction (2) A An
Physical system:
Let the reactant A be the species 1
Let the product An be the species 2
To restrict ourselves to only binary mixture, we shall assume that there
will be no other species
The chemical reaction demands that
N 1 = − nN 2
The above equation simply states that “n” moles of reactant (A) coming
down towards the catalytic surface is equal to “1” mole of product An
going out of the surface
Reaction (3) A An
N 1 = − nN 2 N2 = −
1
N1
n
Diffusion with Heterogeneous n A → An
Reaction (4) A An
cD 12 dx 1
N1 = −
⎡ ( n − 1) ⎤ dz
⎢1 − x1 ⎥
⎣ n ⎦
Diffusion with Heterogeneous n A → An
Reaction (5) A An
The solution:
⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2 A
⎣ 1 − ( n − 1) x 1 / n ⎦ n An
⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥ = K 1 (L) + K 2
⎣ 1 − (n − 1)( 0 ) / n ⎦ n
Diffusion with Heterogeneous
n A→A
Reaction (9) n
The solution:
⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2 A
⎣ 1 − ( n − 1) x 1 / n ⎦ n An
⎛ n ⎞ cD 12 ⎡ 1 ⎤
K 1 = −⎜ ⎟ ln ⎢ ⎥
⎝ n − 1 ⎠ L ⎢⎣ 1 − (n − 1 )x 1, 0 / n ⎥⎦
Diffusion with Heterogeneous
n A→A
Reaction (10) n
z = L; N1 z =L = kcx1 z =L A
An
This is the boundary condition of the fifth kind.
Here k is the chemical reaction rate constant
Diffusion with Heterogeneous
n A→A
Reaction (13) n
The solution:
⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2 A
⎣ 1 − ( n − 1) x 1 / n ⎦ n An
z = L; N1 z =L = kcx1 z =L − K 1 = kcx 1, L
Diffusion with Heterogeneous
n A→A
Reaction (15) n
The solution:
⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2 A
⎣ 1 − ( n − 1) x 1 / n ⎦ n An
K 1 = − kcx 1, L
Diffusion with Heterogeneous
n A→A
Reaction (16) n
⎡ 1 − ( n − 1) x 1, 0 / n ⎤ ( n − 1) kx 1, L
ln ⎢ ⎥ = − ⋅ z A
⎣ 1 − ( n − 1) x 1 / n ⎦ n D 12 An
Remember that x1,L is still unknown at this stage.
But it can be found easily by putting z = L into the
above equation
⎡ 1 − ( n − 1) x 1, L / n ⎤ ( n − 1) ⎛ kL ⎞
ln ⎢ ⎥= ⋅⎜ ⎟ x 1, L
⎣ 1 − ( n − 1) x 1, 0 / n ⎦ n ⎝ D 12 ⎠
⎛ moles of A reacted ⎞
⎜ ⎟ = kC 1
⎝ volume − time ⎠
Isothermal system
dN 1
− − kC1 = 0
dz
Diffusion & Homogeneous Reaction (6)
The Fick’s law
dx 1
N 1 = − cD 12 + x1(N 1 + N 2 )
dz
dC 1
N 1 = − D 12
dz
Substitute the Fick’s law into the mass
dN 1
balance equation, we get: − − kC1 = 0
dz
d 2C1
D 12 2
− kC 1 = 0
dz
This is one of the classic equation in diffusion
and reaction theory!
Diffusion & Homogeneous Reaction (7)
The mass balance equation
d 2C1
D 12 2
− kC 1 = 0
dz
Physical constraints (Boundary conditions)
At the gas-liquid interface, the concentration is
always equal to the solubility
z = 0; C1 = C1, 0 dN 1
At the bottom of the liquid pool, mass can not
− − kC1 = 0
dz
penetrate through it. So the molar flux at the
bottom of the pool is zero.
z = L; dC1 / dz = 0
Diffusion & Homogeneous Reaction (8)
So we have the mass balance equation & the two
necessary boundary conditions
d 2C1
D 12 2
− kC 1 = 0
dz
z = 0; C1 = C1, 0
z = L; dC1 / dz = 0
Solution by the method of characteristics. In this method,
the solution is assumed to take the form: dN 1
− − kC1 = 0
C1 = e λz dz
More about this useful method of characteristics, see the
book Rice and Do “Applied Mathematics and Modeling
for chemical engineers”, Wiley, 1995, page 63
Diffusion & Homogeneous Reaction (9)
The mass balance equation
d 2C1
D 12 2
− kC 1 = 0
dz
If the assumed form C = e λz
1
( )
satisfy 2 λz
d e λz
D12 − ke =0 dN 1
dz 2 − − kC1 = 0
D12 λ2 e λz − ke λz = 0 dz
(D λ − k ) e = 0
12
2 λz
(D λ − k ) = 0
12
2
λ =
2 k
D12
λ=±
k
D12
Diffusion & Homogeneous Reaction (10)
Solution (continued)
d 2C1
D 12 2
− kC 1 = 0
dz
The assumed form C1 = e λz
where
k
λ=±
D12
Since we have two values for the eigenvalue λ, the dN 1
general solution is a linear combination of the − − kC1 = 0
dz
following two solutions
C1 = e λ1 z C1 = e λ 2 z
That is
λ1 z λ2 z So our solution has two constants of
C1 = A e +Be integration, A and B
Diffusion & Homogeneous Reaction (11)
The equation
d 2C1
D 12 2
− kC 1 = 0
dz
The solution
λ1 z λ2 z k
C1 = A e +Be λ=±
D12
Apply the two boundary conditions
z = 0; C1 = C1, 0 C1, 0 = A e λ1 ( 0 ) + B e λ 2 ( 0 ) = A + B
dC1
z = L; dC1 / dz = 0 = A λ 1 e λ1 ( L ) + B λ 2 e λ 2 ( L ) = 0
dz
Diffusion & Homogeneous Reaction (12)
The equation
d 2C1
D 12 2
− kC 1 = 0
dz
The solution
C1 = A e λ1 z + B e λ 2 z λ=±
k
Solution for A and B D12
λ 2eλ 2L e − λL
A = −C1,0 A = C1, 0
λ1e λ1L − λ 2 e λ 2 L e λL + e − λ L
λ1e λ1L e λL
B = C1, 0 B = C1,0
λ1e λ1L − λ 2 e λ 2 L e λL + e − λL
Diffusion & Homogeneous Reaction (13)
So after a long and tedious (but fun) calculus and
algebra, the solution for the concentration distribution
is − λL λL
C1 e e
= λL − λ L e λ z + λ L − λ L e − λ z
C1, 0 e + e e +e
Simplify it C1 e −λ ( L−z ) eλ ( L−z )
= λL − λL + λ L − λL
C1, 0 e + e e +e
C1 e − λ ( L − z ) + e λ ( L − z )
=
C1, 0 e λL + e − λL
[e −λ ( L−z )
+ eλ ( L−z ) ]
C1 2 cosh[λ(L − z )] cosh[λL(1 − z / L)]
= = =
C1, 0 ( λL
e +e − λL
) cosh (λL ) cosh(λL)
2
Diffusion & Homogeneous Reaction (14)
So the final solution is
C1 cosh[λL(1 − z / L)]
=
C1, 0 cosh(λL)
L2
k k L2 D12 Diffusion Time def
λL = L = = = ≡ Da
D12 D12 1 Reaction Time
k To credit German
scientist Damkohler
So we can write solution as
[
C1 cosh Da (1 − z / L)
=
]
C1, 0 cosh Da( )
Diffusion & Homogeneous Reaction (15)
So the final solution is =
[
C1 cosh Da (1 − z / L) ]
C1, 0 cosh Da ( )
With k L2 Diffusion Time
Da = =
D12 Reaction Time
N 1 z = 0 ≈ k L C 1, 0
C1 −z
≈e
k / D12
C1, 0
C 10 D 12
lim N 1 = Da = C 10 k ⋅ D 12
Da >>1 z= 0 L
⎡(W∆zN x ,1 ) ⎤ ⎡(W∆zN x ,1 ) ⎤
⎢ x
⎥ ⎢ x + ∆x
⎥ + 0 = 0
⎢ ⎥ −⎢ ⎥
⎢ ⎥ ⎢ ⎥
⎢⎣ + (W∆ xN )
z ,1 z ⎥
⎦ ⎢⎣ + (W∆xN )
z ,1 z + ∆z ⎥
⎦
Diffusion into a Falling Film (3)
The mass balance equation
⎡(W∆zN x ,1 ) ⎤ ⎡(W∆zN x ,1 ) ⎤
⎢ x
⎥ ⎢ x + ∆x
⎥ + 0 = 0
⎢ ⎥ −⎢ ⎥
⎢ ⎥ ⎢ ⎥
⎢⎣ + (W∆ xN ) ⎦ ⎢⎣
z ,1 z ⎥
+ (W∆xN )
z ,1 z + ∆z ⎥
⎦
W ∆x ∆z
∂N x ,1 ∂N z ,1
+ =0
∂x ∂z
∂C 1
N z ,1 = − D 12 + v z ( x)C 1
∂z
Diffusion into a Falling Film (6)
The mass balance equation
∂N x ,1 ∂N z ,1
+ =0
∂x ∂z
where the fluxes are
∂C1
N x ,1 = −D12
∂x
∂C1
N z ,1 = − D12 + v z ( x ) C1 ≈ v z ( x ) C1
∂z
Substitute these flux equations into the mass balance equation, we get
∂ 2 C1 ∂C 1
D 12 = v ( x )
∂x 2 ∂z
z
Diffusion into a Falling Film (7)
The mass balance equation The heat balance equation
∂ 2 C1 ∂C 1 1 ∂ ⎛ ∂T ⎞ ∂T
= v z (x) α ⎜ r ⎟ = v ( x )
D 12 r ∂r ⎝ ∂r ⎠ ∂z
z
∂x 2 ∂z
∂ 2T ∂T
α 2 = vz (x)
∂x ∂z
Diffusion into a Falling Film (8)
The mass balance equation
∂ 2 C1 ∂C 1
D 12 = v z (x)
∂x 2
∂z
The boundary conditions:
z = 0; C1 = 0
x = 0; C1 = C1, 0
∂C1
x = δ; N1, x = −D12 =0
∂x
∂ 2 C1 ∂C 1
D 12 = v ( x )
∂x 2 ∂z
z
z = 0; C1 = 0
x = 0; C1 = C1, 0
x = ∞; C1 = 0
Diffusion into a Falling Film (9)
Short contact time problem for Transient heat conduction in a
gas absorption in falling film semi-infinite object
∂ 2C1 ∂C 1 ∂ 2 T ∂T
D 12 ≈ v α 2 =
∂x 2
max
∂z ∂x ∂t
z = 0; C1 = 0 t = 0; T = T0
x = 0; C1 = C1, 0 x = 0; T = Ts
x = ∞; C1 = 0 x = ∞; T = T0
Ts
x
Diffusion into a Falling Film (10)
Short contact time problem for Transient heat conduction in a
gas absorption in falling film semi-infinite object
∂ 2C1 ∂C 1 ∂ 2 T ∂T
D 12 ≈ v α 2 =
∂x 2
max
∂z ∂x ∂t
z = 0; C1 = 0 t = 0; T = T0
x = 0; C1 = C1, 0 x = 0; T = Ts
x = ∞; C1 = 0 x = ∞; T = T0
C1 ( x , t ) − C1, 0 ⎛ x ⎞ T( x, t ) − Ts ⎛ x ⎞
= erf ⎜ ⎟ = erf ⎜ ⎟
0 − C1, 0 ⎜ 4D z / v ⎟ T0 − Ts ⎝ 4αt ⎠
⎝ 12 max ⎠
⎡ ⎛ x ⎞⎤
C 1 = C 10 ⎢1 − erf ⎜⎜ ⎟⎟ ⎥
⎢⎣ ⎝ 4 D 12 z / v max ⎠ ⎥⎦
Diffusion into a Falling Film (11)
Short contact time problem for gas absorption in ∂ 2C1 ∂C 1
falling film D 12 ≈ v
∂x 2 ∂z
max
⎡ z = 0; C1 = 0
⎛ x ⎞⎤
C 1 = C 10 ⎢1 − erf ⎜⎜ ⎟⎟ ⎥ x = 0; C1 = C1, 0
⎢⎣ ⎝ 4 D 12 z / v max ⎠ ⎥⎦
x = ∞; C1 = 0
The quantity of interest is the gas absorption rate
into the thin film. It simply is
∂C1
N x ,1 = − D12
x =0
∂x x =0
Diffusion into a Falling Film (12)
Find the derivative
∂C1 ⎛ 2 − η2 ⎞ ⎡ 1 ⎤
⎡ ⎛ x ⎞⎤ = −C10 ⎜ e ⎟⎢ ⎥
C1 = C10 ⎢1 − erf ⎜ ⎟⎥ ∂x ⎝ π ⎠ ⎢⎣ 4D12 z / v max ⎥⎦
⎢⎣ ⎜ 4D z / v ⎟⎥
⎝ 12 max ⎠⎦
∂C1 ∂ ⎡ ⎛⎜ x ⎞⎤
⎟⎥ ∂C1 C10 ⎡ x2 ⎤
= −C10 ⎢erf =− exp ⎢− ⎥
∂x ∂x ⎢⎣ ⎜⎝ 4D12 z / v max ⎟⎥
⎠⎦ ∂x πD12 z / v max ⎣ 4D12 z / v max ⎦
∂C1 ∂
= −C10 [erf (η)]
∂x ∂x η=
x
4D12 z / v max
∂C1 ∂
= −C10 [erf (η)] ∂η
∂x ∂η ∂x
Diffusion into a Falling Film (13)
The partial derivative of C1 with respect to x
∂C1 C10 ⎡ x2 ⎤
=− exp ⎢− ⎥
∂x πD12 z / v max ⎣ 4 D12 z / v max ⎦
∂C C10 D12 ⎡ x2 ⎤
N1 x = 0 = − D12 1 = exp ⎢− ⎥
∂x x =0 πD12 z / v max ⎣ 4 D12 z / v max ⎦ x = 0
C10 D12
N1 x = 0 =
πD12 z / v max
This is the gas absorption flux which is a function of z.
To calculate the mass transfer rate that occurs over the
whole interfacial area, we simply perform an integration
with respect to area
Diffusion into a Falling Film (14)
Therefore the molar flux at the gas-liquid interface is
C10 D12
N1 x = 0 =
πD12 z / v max
The mass transfer rate that occurs over the whole
interfacial area is
L L
D 12 v max
M 1 = W ∫ N x ,1 x= 0 dz = W ∫ C10 dz
0 0
πz
4 D 12 v max
M 1 = (WL) C10
πL
vt
D Species 1 Species 2
Gas Absorption from a Rising Bubble (3)
The physical system: The physical system:
Rising bubble Falling film
vt
L
D
d ⎛ πD3 p 0 ⎞
⎜
dt ⎝ 6 RT⎠
⎟ = −(πD 2
)C10
4D12 v t
πD
⎛ Average ⎞ 4D12 v t
⎜⎜ ⎟⎟ = C10
⎝ molarflux ⎠ πD
Gas Absorption from a Rising Bubble (5)
The mass balance equation around the bubble:
vt
d ⎛ πD3 p 0 ⎞
⎜
dt ⎝ 6 RT⎠
(
⎟ = − πD C10
2
πD
)
4D12 v t
p0 d
(D ) = −C10 2D12 g∆ρD
2RT dt π 9µ
dD
dD C RT 2D12 g∆ρ = −2γ D
= −2 D 10 dt
dt p0 π 9µ
Gas Absorption from a Rising Bubble (6)
SO the final mass balance of the bubble is
dD
= −2 γ D
dt
The initial condition is t = 0; D = D0
The solution:
dD
= − γdt D = D0 − γt
2 D
C10 RT 2D12 g∆ρ
γ=
p0 π 9µ
This solution tells us how the bubble size changes with time. So we can solve
for the time when the bubble completely dissolves
1
t =
*
D0
γ
Gas Absorption from a Rising Bubble (7)
Knowing the bubble size as a function of time
C10 RT 2D12 g∆ρ
D = D0 − γt γ=
p0 π 9µ
we can obtain the terminal velocity as a function of time
vt =
g∆ρD 2 g∆ρ
18µ
=
18µ
( D 0 − γt )
4
dx
dt
= vt =
g∆ρ
18µ
( D 0 − γt )
4
Gas Absorption from a Rising Bubble (8)
Thus the distance traveled by the bubble is
dx
dt
= vt =
g∆ρ
18µ
(
D 0 − γt
4
)
g∆ρ
( )
t
18µ ∫0
4
x= D 0 − γt dt
1 g∆ρ
( ) ( )
t
γ 18µ ∫0
4
x=− D 0 − γt d D 0 − γt
x=−
1 g∆ρ
5γ 18µ
( D 0 − γt ) 5 t
x=
1 g∆ρ ⎡
⎢
5γ 18µ ⎣
(
D0 ) −(
5
)
D 0 − γt ⎤
5
⎥⎦
Gas Absorption from a Rising Bubble (9)
At the time when the bubble completely dissolve
1
t* = D0
γ
⎛ π ⎞ ⎛ g∆ρD5o ⎞ ⎛ p / RT ⎞
H = ⎜⎜ ⎟⋅⎜ ⎟⋅⎜ 0 ⎟
⎟ ⎜ ⎟ ⎜⎝ C10 ⎟⎠
⎝ 30 2 ⎠ ⎝ µD12 ⎠
C10 RT 2D12 g∆ρ
γ=
p0 π 9µ
Diffusion and Reaction in a Porous
Catalyst (1)
Porous Catalysts: very complex because
Pores of different size and shape
Pores are tortuous
Resistance to mass transfer
∂C ∂T
J = −D eff q = −k eff
∂r ∂r
D eff = f (D12 , D K , ε, τ )
Extensive research was conducted in the 60 and 70 by engineers, and one of
the simple formulas is given below for the effective diffusivity
ε
D eff = D c
τ
Diffusion and Reaction in a Porous
Catalyst (9)
The effective diffusivity
ε
D eff = D c
τ
Where ε is the particle porosity. This is to account for the fact that only a
fraction of ε of the cross sectional area is available for mass transfer
The parameter τ is the tortuosity factor. It accounts for the zig-zag pattern of
the pore.
The parameter Dc is called the combined diffusivity. It accounts for two
mechanisms for diffusion in pore, namely molecular diffusion and Knudsen
diffusion
Diffusion and Reaction in a Porous
Catalyst (9)
ε
The effective diffusivity D eff = Dc
τ
The combined diffusivity is given by:
1 1 1
= +
D eff ,1 D12 D K ,1
Where D12 is the usual binary diffusivity
And DK is the Knudsen diffusivity
The molecular diffusivity can be found in any books or handbook (such as
Perry) or it can be calculated from Chapman-Enskog equation
The Knudsen diffusivity is calculated from
Order of magnitude
ε 0.2 – 0.7
τ 2-6
D12 0.1 - 2 cm2/s
DK 0.1 - 100 cm2/s
Diffusion and Reaction in a Porous
Catalyst (11)
ε
The effective diffusivity D eff = Dc
τ
The combined diffusivity is given by:
1 1 1
= +
D eff ,1 D12 D K ,1
Diffusivity P T r M
Binary diffusivity P-1 T1.75 r0 1 1
+
M1 M2
Knudsen diffusivity P0 T0.5 r1 1
M1
Diffusion and Reaction in a Porous
Catalyst (12)
ε
The effective diffusivity D eff = Dc
τ
The combined diffusivity is given by:
1 1 1
= +
D eff ,1 D12 D K ,1
Controlling mechanism
Molecular diffusion dominates in
large pores and high pressure Diffusivity P T r M
Knudsen diffusion dominates in small Binary P-1 T1.75 r0 1 1
+
pores and very low pressure diffusivity M1 M 2
Knudsen P0 T0.5 r1 1
diffusivity M1
Diffusion and Reaction in a Porous
Catalyst (13)
Reaction rate
Since reaction in a porous catalyst occurs on surface, the reaction rate is usually
(but not always) defined as mole reacted per unit surface area and per unit time
⎡ moles reacted ⎤
ℜ( c ) ⎢⎣ surface area - time ⎥⎦
⎡ moles reacted ⎤
ℜ(C) = kC ⎢⎣ surface area - time ⎥⎦
With this definition of the reaction rate, the reaction rate constant of the first-order
reaction has units of m/s
Diffusion and Reaction in a Porous
Catalyst (14)
Summary
ε
Diffusion rate D eff = D c
τ
∂C ⎡ moles transported ⎤ 1 1 1
J = − D eff ⎢ total cross section area - time ⎥ = +
∂r ⎣ ⎦ D eff ,1 D12 D K ,1
Reaction rate
⎡ moles reacted ⎤
ℜ(C) = kC ⎢⎣ surface area - time ⎥⎦
[( )
4πr 2 N r = r − 4πr 2 N r = r + ∆r − 4πr 2 ∆r ρ pSg kC = 0] r
4π ∆r
r 2 N r = r + ∆r − r 2 N r = r
− − r 2ρ pSg kC = 0
∆r
∂ 2
−
∂r
( )
r N − r 2ρ pSg kC = 0
Diffusion and Reaction in a Porous
Catalyst (16)
The mass balance equation
∂ 2
−
∂r
( )
r N − r 2ρ pSg kC = 0 ∆r
For simplicity, we shall assume the boundary condition of the first kind at the
catalyst surface. In general, you should use the boundary condition of the third
kind
∂C
r = R; − D eff
∂r r = R
(
= k m C r =R − C0 )
Diffusion and Reaction in a Porous
∆r
Catalyst (18)
So, the mass balance equation
D eff ∂ ⎛ 2 ∂C ⎞
⎜r ⎟ − ρ pSg kC = 0 r
r ∂r ⎝ ∂r ⎠
2
∂C
r = 0; =0
∂r
r = R; C = C 0 (known bulk concentration )
It is much more convenient and compact if we cast the above mass balance
equation into non-dimensional form. To do this we scale the concentration
against the bulk concentration C0 and the radial distance against the particle
radius
r C
x= ; y=
R C0
Diffusion and Reaction in a Porous
∆r
Catalyst (19)
Let us dimensionalize the mass balance
equation, and something will evolve naturally
r
out of this process
D eff ∂ ⎛ 2 ∂C ⎞
⎜r ⎟ − ρ pSg kC = 0
r ∂r ⎝ ∂r ⎠
2
r C
x= ; y=
R C0
D eff ∂ ⎡ 2 ∂ (C 0 y ) ⎤
⎢ (Rx ) ⎥ − ρ pSg k (C 0 y ) = 0
(Rx ) ∂Rx ⎣
2
∂ (Rx ) ⎦
1 ∂ ⎡ 2 ∂y ⎤ ⎛⎜ ρ pSg k R ⎞⎟
2
D eff 1 ∂ ⎡ 2 ∂y ⎤
⎢ x ⎥ − ρ pSg ky = 0 ⎢ x ⎥ − y=0
R x ∂x ⎣ ∂x ⎦
2 2 2 ⎜
x ∂x ⎣ ∂x ⎦ ⎝ D eff ⎠ ⎟
Diffusion and Reaction in a Porous
∆r
Catalyst (20)
The mass balance equation is …..
1 ∂ ⎡ 2 ∂y ⎤ ⎛⎜ ρ pSg k R ⎞⎟
2
r
⎢ x ⎥ − y=0
⎜
x ∂x ⎣ ∂x ⎦ ⎝ D eff ⎠
2 ⎟
= ⎝ eff ⎠ ≡
D Diffusion time
φ2 =
D eff ⎛ 1 ⎞ Reaction time
⎜ ⎟
⎜ρ S k⎟
⎝ p g ⎠
If φ << 1 (diffusion time is small compared to reaction time), we would expect
uniform concentration profile and the reaction is kinetically-controlled
If φ >> 1 (diffusion time is greater than reaction time), we would expect a very
sharp concentration profile and the reaction is called difuusion-controlled
Diffusion and Reaction in a Porous
∆r
Catalyst (22)
So the mass balance equation is …..
1 ∂ ⎡ 2 ∂y ⎤ 2
⎢ x ⎥ −φ y = 0 r
x ∂x ⎣ ∂x ⎦
2
Solution?
Introduce a new variable
u
y=
x
Substitute this into the above mass balance equation
1 ∂ ⎡ 2 ∂ (u / x ) ⎤ 2 u
x −φ =0
x 2 ∂x ⎢⎣ ∂x ⎥⎦ x
1 ∂ ⎡ 2 ⎛ 1 ∂u u ⎞⎤ 2 u 1 ∂ ⎛ ∂u ⎞ 2u
x ⎜ − ⎟ −φ =0 ⎜ x − u ⎟−φ =0
x 2 ∂x ⎢⎣ ⎝ x ∂x x 2 ⎠⎥⎦ x ∂x ⎝ ∂x ⎠
2
x x
Diffusion and Reaction in a Porous
∆r
Catalyst (23)
Solution (continued)
1 ∂ ⎛ ∂u ⎞ 2u r
⎜ x − u ⎟−φ =0
x 2 ∂x ⎝ ∂x ⎠ x
1 ⎛ ∂u ∂ 2 u ∂u ⎞ 2 u
⎜ + x 2 − ⎟⎟ − φ =0
x 2 ⎜⎝ ∂x ∂x ∂x ⎠ x
1 ∂ 2u 2 u
− φ =0
x ∂x 2
x
∂ 2u
− φ 2
u=0
∂x 2
r = R; C = C0 x = 1; y =1 x = 1; u =1
Catalyst (26)
The solution for the non-dimensional concentration is r
1 sinh (φx )
y=
x sinh (φ)
The reaction rate in the catalyst particle is simply to molar flux at the
surface of the catalyst
∂C ⎡ moles reacted ⎤
N R = −D eff ⎢ area of catalyst - time ⎥
∂r r = R ⎣ ⎦
Catalyst (27)
Reaction rate per particle r
⎛ ∂C ⎞ ⎡ moles reacted ⎤
( ⎜ )
W = 4πR ⎜ − D eff
2
⎟⎟
∂r r = R ⎠ ⎢ particle - time ⎥
⎝ ⎣ ⎦
Catalyst (28)
The reaction rate per particle is r
Catalyst (29)
The reaction rate per particle is r
(
W = − 4πR 2 )( )
ρ pSg D eff k C 0
D = f (C, ∂C / ∂x , T )
Diffusion through a Polymer Film (2)
This last example will show you how to determine the intra-
membrane diffusivity.
The method is the time-lag method, developed by Daynes in 1920
who studied the permeation of gases through rubbery membranes
used in balloons
Diffusion through a Polymer Film (3)
The time lag method is quite simple.
It consists of two chambers separated by the tested membrane
The top chamber is maintained at constant pressure P0
The pressure of the bottom chamber is monitored with respect to time
time
Diffusion through a Polymer Film (4)
The shell is drawn inside the membrane
The mass balance equation is
∂C ∂ 2C
=D 2
∂t ∂x
The initial condition and boundary conditions are:
t = 0; C=0
x = 0; C = HP0
x = L; C≈0
A R T P0 ⎧⎪ 2H L2 ∞
cos(nπ) ⎡ ⎛ n 2 π 2 D ⎞⎤ ⎫⎪
P= ⎨H D t +
⎪⎩ π2
∑ ⎢ 1 − exp⎜⎜ − t ⎟⎟⎥ ⎬
⎠⎦ ⎪⎭
2 2
VL n =1 n ⎣ ⎝ L
Diffusion through a Polymer Film (6)
So the solution for the pressure of the bottom
chamber is
A R T P0 ⎧⎪ 2H L2 ∞
cos(nπ) ⎡ ⎛ n 2 π 2 D ⎞⎤ ⎫⎪
P= ⎨H D t +
⎪⎩ π2
∑ ⎢ 1 − exp⎜⎜ − t ⎟⎟⎥ ⎬
⎠⎦ ⎪⎭
2 2
VL n =1 n ⎣ ⎝ L
time