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Transport Phenomena

Section 3: Mass Transfer


D. D. Do
University of Queensland
Mode of Mass Transfer
† Diffusion:
„ Molecular diffusion
„ Knudsen diffusion
† Convection

† Diffusion is more complicated than viscous flow and heat


conduction because we have to deal with mixture (more than
one component)
„ But this is what chemical engineers like!
Definitions of Concentration, Velocity
and Fluxes
† Concentration Mass concentration mass of j
ρj =
volume of solution
„ Solution of one
phase whether it Molar concentration ρj moleof j
Cj = =
be gas, liquid or Mj volumeof solution
solid phase Mass fraction ρj ρj mass of j
ωj = = =
ρ n

∑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

† The molar flux is (molar rate per unit area)


n

∑C v
k =1
k k
Velocities and Average Velocities (2)
† Different components move at different velocities
2 v2

1
v1

† The local mass velocity is defined as a velocity


„ If we multiply it by the total mass concentration, we get the total mass
flux n n

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

† The local molar velocity is defined as a velocity


„ If we multiply it by the total molar concentration, we get the total
molar flux
n n
n ∑C vk ∑C vk
Cv = ∑ C k v k
k k n n
Ck
v =
* k =1
n
= k =1
=∑ vk = ∑ x k vk
∑ Ck
k =1
C k =1 C k =1

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

„ In this example, both components move to the right according to the


person standing on a fixed position. However, according to the
person riding with the flow, component 1 moves to the right while
component 2 moves to the left
Diffusion Velocities (2)
† This gives rise to the need to define the so-called diffusion
velocity
„ There are two diffusion velocities
† Diffusion velocity relative to the mass average velocity
† Diffusion velocity relative to the molar average velocity

⎛ diffusion velocity of species j⎞ ⎛ diffusion velocity of species j⎞


vj − v ≡ ⎜ ⎟ v j − v* ≡ ⎜ ⎟
⎝ with respect to v ⎠ ⎝ with respect to 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 ⎠

„ which is the number of moles of the component j transported per unit


time and per unit cross sectional area perpendicular to the velocity vj
Diffusion Mass and Molar Fluxes (1)
† The diffusion mass flux is defined the flux relative to the bulk
motion of the solution

(
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 *)

This is necessary for the diffusion analysis

This is useful for engineering calculation of mass transfer

† So we need to relate these two most important quantities in


mass transfer.
„ The relationship between the molar flux and the molar diffusive flux is
n
Jk = Nk − xk ∑ N j
j= 1
Diffusion Flux vs Flux (2)
† The relationship between the molar flux and the molar
diffusive flux is
n
Jk = Nk − xk ∑ N j
j= 1 n
† Proof: Always go back to definition ∑C v j j

(
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

† What it means is that the two diffusion equations


dx1
J 1 = − cD12
dz

dx 2
J 2 = −cD 21
dz
„ are not independent. So only one is used. Either one will do.

† For three-dimensional coordinates, the Fick’s law equation is

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

† So we need to find another equation. This equation is specific to a given


system. More about this later when we deal with a number of examples.
Diffusion Coefficient
† Units ⎡ m2 ⎤ State Order of magnitude (cm2/s)
D12 ≡⎢ ⎥
⎣ sec ⎦
Gas 0.1 - 1
† Order of magnitude
Liquid 1 × 10-7 – 1 × 10-5

Solid 1 × 10-12 – 1 × 10-7

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

† Another form of the Stefan-Maxwell equation is

− c ∇x i = ∑
n
(x J
j i − xi J j )
j=1 D ij

† Details of this exact Stefan Maxwell equation can be found in D. D. Do,


“Adsorption Analysis”, Imperial College Press, New Jersey, 1998,
Chapter 8
First Principles for Binary Mixtures (1)
† The procedure is identical to what you have learnt before in
momentum and heat transfers
„ Draw physical diagram and then a thin shell whose surfaces are
perpendicular to the transport directions
„ Set up the mass balance equation around the shell
⎛ Rate of ⎞ ⎛ Rate of ⎞ ⎛ Rate of mass⎞
⎜ ⎟ −⎜ ⎟ +⎜ ⎟ = ( Accummulation)
⎝ mass in ⎠ ⎝ mass out⎠ ⎝ production ⎠

„ 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 ⎠

† To find K1 and K2, you apply the two


boundary conditions z1
⎛ 1 ⎞
@ z = z1 ; cD 12 ln ⎜ ⎟ = K1z1 + K 2
⎝ 1 − x 1, 0 ⎠ 0
⎛ 1 ⎞
@ z = z2 ; cD 12 ln ⎜ ⎟ = K1z 2 + K 2
⎝ 1 − x 1, L ⎠

† So you can solve for K1 and K2


Diffusion in a Stefan tube (8)
† Solution cD ln ⎛⎜ 1 ⎞⎟ = K z + K
⎝ 1 − x1 ⎠
12 1 2
z2
† K1 and K2
cD 12 ⎛ 1 − x 1, 0 ⎞
K1 = ln ⎜ ⎟
z 2 − z 1 ⎝ 1 − x 1, L ⎠ z1
⎛ 1 ⎞ cD 12 z 1 ⎛ 1 − x 1, 0 ⎞
K 2 = cD 12 ln ⎜ ⎟− ln ⎜ ⎟
⎝ 1 − x 1, L ⎠ z 2 − z 1 ⎝ 1 − x 1, L ⎠
0
† So the concentration distribution is
( z − z1 )/ ( z 2 − z1 )
⎛ 1 − x 1 ⎞ ⎛ 1 − x 1,L ⎞
⎜ ⎟ =⎜ ⎟
⎝ 1 − x 1,0 ⎠ ⎝ 1 − x 1,0 ⎠
Diffusion in a Stefan tube (9)
† So the final solution for the concentration
distribution is z 2
( z − z1 )/ ( z 2 − z1 )
⎛ 1 − x 1 ⎞ ⎛ 1 − x 1,L ⎞
⎜ ⎟ =⎜ ⎟
⎝ 1 − x 1,0 ⎠ ⎝ 1 − x 1,0 ⎠
z1
† To find the evaporation flux, we simply
apply the Fick’s law
cD 12 dx 1 0
N1 = −
1 − x 1 dz
„ This means that we have to take the derivative of
the mole fraction x1 with respect to distance z!!
Diffusion in a Stefan tube (10)
† Let us find the flux formally
( z − z1 )/ ( z 2 − z1 )
⎛ 1 − x 1 ⎞ ⎛ 1 − x 1,L ⎞ z2
⎜ ⎟ =⎜ ⎟
⎝ 1 − x 1, 0 ⎠ ⎝ 1 − x 1, 0 ⎠

† Taking logarithm both side


⎛ 1 − x1 ⎞ ⎧⎪⎛ 1 − x ⎞ (z − z1 )/ (z 2 − z1 ) ⎫⎪ z1
ln⎜⎜ ⎟ = ln ⎨⎜

1, L
⎜ 1− x ⎟
⎟ ⎬
⎝ 1 − x 1, 0 ⎠ ⎪⎩⎝ 1, 0 ⎠ ⎪⎭

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 ⎟⎠

† Substitute this into the Fick’s law


z1
cD 12 dx 1
N1 = −
1 − x 1 dz
0
† The evaporation flux is
cD12 ⎛⎜ 1 − x1,L ⎞⎟
N1 = ln
z 2 − z1 ⎜⎝ 1 − x1, 0 ⎟⎠

† This is a long, but formal, way of getting the flux


Diffusion in a Stefan tube (12)
† However there is a short cut. Remember that
during the integration of the mass balance we
got: z2
cD 12 dx 1
= K1
1 − x 1 dz

† And K1 was found from the application of the z


1
boundary condition as
cD12 ⎛ 1 − x 1,0 ⎞
K1 = ln⎜ ⎟
z 2 − z1 ⎝ 1 − x 1,L ⎠ 0

† Therefore the evaporation flux is


cD12 ⎛⎜ 1 − x1,L ⎞⎟
N1 = ln
z 2 − z1 ⎜⎝ 1 − x1, 0 ⎟⎠
Diffusion in a Stefan tube (13)
† So the solution for the evaporation flux is
cD12 ⎛⎜ 1 − x1,L ⎞⎟ z2
N1 = ln⎜
z 2 − z1 ⎝ 1 − x1, 0 ⎟⎠

† If the gas 2 is sweeping past the tube fast


enough, the concentration of the species 1 at z1
the mouth is effectively zero. Hence the
evaporation rate is
cD 12 ⎛ 1 ⎞ 0
N1 = ln ⎜ ⎟
z 2 − z 1 ⎝ 1 − x 1, 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 ⎠

† The total flux is

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 ⎠

† Therefore you need to write a mass balance z1


around the liquid
d (Sz 1ρ L )
= − SM 1 N 1
dt 0
d (Sz 1ρ L ) ( P / RT ) D 12 ln ⎛ 1 ⎞
= − SM 1 ⎜ ⎟
dt z 2 − z1 ⎝ 1 − p 10 / P ⎠

† This is a differential equation with respect to t


Diffusion in a Stefan tube (16)
† Differential equation for the liquid level with z2
respect to t
d (Sz 1ρ L ) ( P / RT ) D 12 ln ⎛ 1 ⎞
= − SM 1 ⎜ ⎟
dt z 2 − z1 ⎝ 1 − p 10 / P ⎠
z1
† The initial condition is
t = 0; z 1 = z 1, 0
0

† 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!!

† Conclusion: DIFFUSION IS A SLOW


PROCESS. Get rid of it IF YOU CAN
Dissolution of a Sphere (1)
† Physical system: Sparingly soluble sphere in a surrounding
fluid of infinite extent

„ The object (1) dissolves into a liquid (2)


„ The solubility is C10
r
∆r

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

† Substitute the Fick’s law into the mass balance equation


d ⎛ 2 dx 1 ⎞
⎜ r cD 12 ⎟=0
dr ⎝ dr ⎠
r
Dissolution of a Sphere (4)
† So the final form of the mass balance equation is
d ⎛ 2 dx 1 ⎞ d⎛ 2 dC1 ⎞
⎜ r cD ⎟=0 ⎜ r D ⎟=0
dr ⎝ dr ⎠
12 12
dr ⎝ dr ⎠
† The boundary conditions are:
r = R; C 1 = C 1, 0 r = ∞; C1 = 0
† The concentration distribution
R
C 1 = C 10
r
† The dissolution rate dx1 dC1
„ Back to the Fick’s law: N1 ≈ −cD12 = − D 12
dr dr
„ The dissolution rate is simply the flux at the surface of the object
dC D C
N1 r = R ≈ − D12 1 = 12 10
dr r = R R
r
Dissolution of a Sphere (5)
† Very often the dissolution is calculated by using the concept of mass
transfer coefficient:

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

„ This group is known as the Sherwood number to describe the mass


transfer coefficient
Dissolution of a Sphere (6)
† So the Sherwood number for a stagnant environment is
k m (2 R )
=2
D12

† Recall the equivalent number in heat transfer is Nu


h ( 2R )
=2
kf

† 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

„ This equation basically provides the additional equation to the Fick’s


law equation
Diffusion with Heterogeneous n A → An

Reaction (3) A An

† The shell balance equation:


„ Setting a shell at the distance z in the stagnant film
dN 1
− =0
dz
† The Fick’s law
dx 1
N 1 = − cD 12 + x1 (N 1 + N 2 )
dz
„ This equation involves two unknown variables N1 and N2. We need
one more equation, and that equation is specific to this problem, which
is the reaction stoichiometry

N 1 = − nN 2 N2 = −
1
N1
n
Diffusion with Heterogeneous n A → An

Reaction (4) A An

† The mass balance equation:


dN 1
− =0
dz 1
N 2 = − N1
† The Fick’s law n
dx 1
N 1 = − cD 12 + x1 (N 1 + N 2 )
dz
„ Substitute the stoichiometry relation into the Fick’s law, you can now
solve for the molar flux N1 in terms of the concentration gradient

cD 12 dx 1
N1 = −
⎡ ( n − 1) ⎤ dz
⎢1 − x1 ⎥
⎣ n ⎦
Diffusion with Heterogeneous n A → An

Reaction (5) A An

† The mass balance equation:


dN 1
− =0
dz
† The Fick’s law
cD 12 dx 1
N1 = −
⎡ ( n − 1) ⎤ dz
⎢1 − x1 ⎥
⎣ n ⎦
† The mass balance equation, then, gives:
cD 12 dx 1
N1 = − ≡ −K1
⎡ (n − 1) ⎤ dz
⎢⎣1 − n x 1 ⎥⎦
Diffusion with Heterogeneous
Reaction (6)
† The mass balance equation:
cD 12 dx 1
N1 = − ≡ −K1
⎡ (n − 1) ⎤ dz
⎢⎣1 − n x 1 ⎥⎦
† Now we pose the boundary conditions
n A→An
z = 0; x1 = x10
z = L; x1 = 0
A
An
Diffusion with Heterogeneous
n A→A
Reaction (7) n

† The mass balance equation:


cD 12 dx 1
N1 = − ≡ −K1
⎡ (n − 1) ⎤ dz
A
⎢⎣1 − n x 1 ⎥⎦ An

† Integrating the mass balance equation one more time


⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2
⎣ 1 − ( n − 1) x 1 / n ⎦ n

„ We have two constants of integration, and we also have two boundary


conditions
Diffusion with Heterogeneous
n A→A
Reaction (8) n

† The solution:
⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2 A
⎣ 1 − ( n − 1) x 1 / n ⎦ n An

† Applying the two boundary conditions


⎡ ⎤ ( n − 1)
z = 0; x1 = x10 cD 12 ln ⎢
1
⎥= K 1 (0) + K 2
z = L; x1 = 0 ⎣⎢ 1 − (n − 1)x 1, 0 / n ⎥⎦ n

⎡ 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

† Solving for K1 and K2, we get


Remember that N1 = - K1; So
⎡ 1 ⎤ the negative of the constant
K 2 = cD 12 ln ⎢ ⎥
⎣⎢ 1 − (n − 1 )x 1, 0 / n ⎥⎦
K1 is simply the flux

⎛ 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

† The solution for the concentration distribution:


( 1− z / L )
⎡ ( n − 1) ⎤ ⎡ ( n − 1) ⎤
⎢1 − x 1 ⎥ = ⎢1 − x 10 ⎥ A
⎣ n ⎦ ⎣ n ⎦ An
† The molar flux across the stagnant film is the
negative of the constant K1:

⎛ n ⎞ cD12 ⎡ 1 ⎤ SO THIS IS THE


N1 = ⎜ ⎟ ln ⎢ ⎥
⎝ n − 1 ⎠ L ⎢⎣1 − (n − 1)x 1, 0 / n ⎥⎦ REACTION RATE
PER UNIT AREA
OF THE CATALYST
„ This molar flux tells you how many moles of
reactant passing through the stagnant film per
unit area and unit time. This is EXACTLY
equal to the rate of reaction at the surface
Diffusion with Heterogeneous
Reaction (11)
† We just completed the analysis of diffusion and surface
reaction for the case of extremely fast reaction, and you
probably have noted that
„ The reaction rate does not involve the rate constant of chemical
reaction.
„ This is so because reaction is so fast and since it is in series with a
diffusion process, the slow step is the controlling step, which is the
diffusion process.
„ Therefore the rate of reaction only involves the diffusion
characteristics, D12, and the reaction stoichiometry

† Let’s have a look at the general case of finite reaction rate at


the surface
Diffusion with Heterogeneous
Reaction (12)
† The mass balance equation:
cD 12 dx 1
N1 = − ≡ −K1
⎡ (n − 1) ⎤ dz
⎢⎣1 − n x 1 ⎥⎦
† Now we pose the boundary conditions
n A→An
z = 0; x1 = x1,0

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 mass balance equation:


cD 12 dx 1
N1 = − ≡ −K1
⎡ (n − 1) ⎤ dz
A
⎢⎣1 − n x 1 ⎥⎦ An

† Integrating the mass balance equation one more time


⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2
⎣ 1 − ( n − 1) x 1 / n ⎦ n

„ We have two constants of integration, and we also have two boundary


conditions
Diffusion with Heterogeneous
n A→A
Reaction (14) n

† The solution:
⎡ 1 ⎤ ( n − 1)
cD 12 ln ⎢ ⎥= K1z + K 2 A
⎣ 1 − ( n − 1) x 1 / n ⎦ n An

† Applying the two boundary conditions


⎡ 1 ⎤ ( n − 1)
z = 0; x1 = x10 cD 12 ln ⎢ ⎥= K 1 (0) + K 2
⎣⎢ 1 − (n − 1)x 1, 0 / n ⎥⎦ n

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

† Solving for K1 and K2, we get


⎡ 1 ⎤
K 2 = cD 12 ln ⎢ ⎥
⎣⎢ 1 − (n − 1 )x 1, 0 / n ⎥⎦

K 1 = − kcx 1, L
Diffusion with Heterogeneous
n A→A
Reaction (16) n

† The solution for the concentration distribution:

⎡ 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 ⎠

„ This is a nonlinear equation in terms of x1,L.


Diffusion with Heterogeneous
Reaction (17)
† How to get x1,L?
⎡1 − ( n − 1) x 1,L / n ⎤ ( n − 1) ⎛ kL ⎞
ln ⎢ ⎥= ⋅⎜ ⎟ x 1,L
⎣ 1 − ( n − 1) x 1,0 / n ⎦ n ⎝ D 12 ⎠

† Knowing this concentration


at the catalytic surface, the
reaction rate is
N1 z=L
= kcx 1, L
„ Thus the reaction rate in the
case of finite reaction is a
function of the reaction rate
constant and the diffusion
coefficient
Diffusion with Heterogeneous
Reaction (18)
† Equation for x1,L
⎡1 − ( n − 1) x 1,L / n ⎤ ( n − 1) ⎛ kL ⎞
ln ⎢ ⎥= ⋅⎜ ⎟ x 1,L
⎣ 1 − ( n − 1) x 1,0 / n ⎦ n ⎝ D 12 ⎠

† This equation involves a


non-dimensional group
⎛ kL ⎞ chemical reaction rate
⎜ ⎟≡
⎝ D 12 ⎠ diffusion rate

„ Which describes the interplay


between the reaction rate and
the diffusion rate
Diffusion & Homogeneous Reaction (1)
† Let us now consider a new example where we have diffusion
and reaction occurring simultaneously, rather than reaction at
the boundary.
Diffusion & Homogeneous Reaction (2)
† The system: Absorption and reaction
Diffusion & Homogeneous Reaction (3)
† The system: Absorption and reaction
„ Gas A dissolves sparingly in liquid B
„ Dissolved A reacts with B, according to a first
order chemical reaction

⎛ moles of A reacted ⎞
⎜ ⎟ = kC 1
⎝ volume − time ⎠

„ Isothermal system

† Let the species A be 1; and the species B be 2


Diffusion & Homogeneous Reaction (4)
† The system: Absorption and reaction
„ Let us check the assumption “Gas A
dissolves sparingly in liquid B”
„ At 1 atm and ambient temperature (King,
“Separation Processes, McGraw Hill, pg 273)
Gas Mole fraction
Sulfur dioxide 0.03
Chlorine 0.0017
Hydrogen sulfide 0.002
Carbon dioxide 0.00062
Ethylene 0.0001
Carbon monoxide 0.000018
„ Solubility, in general, increases with pressure
and decreases with temperature
Diffusion & Homogeneous Reaction (5)
† The system: Absorption and reaction
„ Shell mass balance

⎛ Rate of ⎞ ⎛ Rate of ⎞ ⎛ Rate of mass⎞


⎜ ⎟ −⎜ ⎟ +⎜ ⎟ = ( Accummulation)
⎝ mass in ⎠ ⎝ mass out⎠ ⎝ production ⎠

(SN1 ) z − (SN1 ) z+ ∆z − (S∆z)kC1 = 0


S ∆z

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

„ is the solution to the mass balance equation, it must

( )
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)

† Let us have a good look at the group 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

† What does this group tell us?


„ When Da << 1: the diffusion time is much smaller
than the reaction time, we would expect
† The concentration distribution is uniform
† The absorption rate is controlled by reaction
„ When Da >> 1: the diffusion time is much greater
than the reaction time, we would expect
† The concentration distribution is very sharp and
localized near the gas-liquid interface
† The absorption rate is controlled by diffusion and
reaction
Diffusion & Homogeneous Reaction (16)
† So the final solution is =
[
C1 cosh Da (1 − z / L) ]
C1, 0 (
cosh Da )
„ with k L2 Diffusion Time
Da = =
D12 Reaction Time

† The absorption rate per unit interfacial area is just


simply the molar flux at the gas liquid interface
dC 1
N 1 z = 0 = − D 12
dz z = 0
C D
N 1 z = 0 = 10 12 Da ⋅ tanh Da
L
( )
C 10 D 12 kL2 ⎛ kL2 ⎞
N 1 z= 0 = ⋅ tanh ⎜⎜ ⎟

L D 12 ⎝ D 12 ⎠
Diffusion & Homogeneous Reaction (17)
† Summary
[
C1 cosh Da (1 − z / L)
=
]
C1, 0 cosh Da ( )
N1 z=0 =
C 10 D 12
L
Da ⋅ tanh ( Da )
k L2 Diffusion Time
Da = =
D12 Reaction Time
Diffusion & Homogeneous Reaction (18)
† Special case: Da << 1
C1
≈1
C1, 0

N 1 z = 0 ≈ k L C 1, 0

† The rate of absorption is controlled


purely by chemical reaction
Diffusion & Homogeneous Reaction (19)
† Special case: Da >> 1

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

† When the reaction is very fast, we see that the


absorption rate is
„ proportional to the square root of reaction rate
constant and diffusivity
„ Independent of the size of the pool
Diffusion into a Falling Film (1)
† Now we shall deal with combination of diffusion and
convection

† The physical system is the gas absorption in a falling film


„ Flow of liquid film is laminar
„ No end effects
„ Solubility is constant
Diffusion into a Falling Film (2)
† Gas absorption in a falling film
„ Shell balance equation

⎛ Rate of ⎞ ⎛ Rate of ⎞ ⎛ Rate of mass⎞


⎜ ⎟ −⎜ ⎟ +⎜ ⎟ = ( Accummulation)
⎝ mass in ⎠ ⎝ mass out⎠ ⎝ production ⎠

⎡(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

† This is the mass balance equation in terms of fluxes. What needs


to done is to relate these fluxes in terms of concentration
Diffusion into a Falling Film (4)
† The mass balance equation ∂N x ,1 ∂N z ,1
+ =0
∂x ∂z
† The molar flux in the x-direction is given by the Fick’s law
∂ C1
N x ,1 = − D 12 + x 1 ( N x ,1 + N x , 2 )
∂x
„ Since most gases dissolve sparingly in liquid, the bulk flow
(second term in the above equation) is negligible compared to
the diffusive term
† The molar flux in the z-direction is also by the Fick’s law
∂C 1
N z ,1 = − D 12 + x 1 ( N z ,1 + N z ,2 )
∂z
Diffusion into a Falling Film (5)
† The molar flux in the z-direction is also by the Fick’s law
∂C 1
N z ,1 = − D 12 + x 1 ( N z ,1 + N z ,2 )
∂z
† By definition of flux
N z ,1 = C 1 v z ,1 ; N z ,2 = C 2 v z ,2
† The Fick’s law can now be written as
∂C 1
N z ,1 = − D 12 + x 1 ( C 1 v z ,1 + C 2 v z ,2 )
∂z But
∂C 1 ⎛ C 1 v z ,1 + C 2 v z ,2 ⎞
N z ,1 = − D 12 + x1 ⎜ ⎟ (C 1 + C 2 ) ⎛ C 1 v z ,1 + C 2 v z ,2 ⎞
⎜ ⎟ = v z (x)
∂z ⎝ C1 + C 2 ⎠ ⎝ C1 + C 2 ⎠

∂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

† Solution of this set of equations is possible, but let us consider the


case of short contact time.
„ The dissolved species only travels a short distance into the bulk liquid
Diffusion into a Falling Film (8)
† Short contact time problem

∂ 2 C1 ∂C 1
D 12 = v ( x )
∂x 2 ∂z
z

„ Dissolved species only feel a convective motion of vmax


velocity, and the plate seems to be far away. So the
mass balance equation and three boundary conditions
are replaced by
∂ 2C1 ∂C 1
D 12 ≈ v
∂x 2 ∂z
max

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 ∂ ⎡ ⎛ ⎞⎤ ∂C1 C10


=− e −η
2
x
= C10 ⎢1 − erf ⎜ ⎟⎥
∂x ∂x ⎢⎣ ⎜ 4D z / v ⎟⎥ ∂x πD12 z / v max
⎝ 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 ⎦

† Therefore the molar flux at the gas-liquid interface is

∂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

† Hence the average molar flux into the falling film is


M1 4D12 v max
N ave = = C10
WL πL END
Gas Absorption from a Rising Bubble (1)
† The physical system:
„ A column of liquid (species 2)
„ A rising bubble containing pure species 1
„ Mass transfer is by absorption of
component 1 into the liquid 2

† Given a bubble of initial size R0


injected into the column, what is the
distance that the bubble can travel
before it completely dissolves?
Gas Absorption from a Rising Bubble (2)
† The physical system:
„ A column of liquid (species 2)
„ A rising bubble containing pure species 1
„ Mass transfer is by absorption of component 1 into the liquid 2

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

⎛ Average ⎞ 4D12 v t ⎛ Average ⎞ 4D12 v max


⎜⎜ ⎟⎟ = C10 ⎜⎜ ⎟⎟ = C10
⎝ molarflux ⎠ πD ⎝ molarflux ⎠ πL
Gas Absorption from a Rising Bubble (4)
† The physical system: † So we know the average flux of
„ Rising bubble mass transfer from the bubble to
the surrounding
vt „ The remaining task is to carry out
the mass balance around the
bubble to find out how fast the
bubble will shrink
D
† The mass balance around the
bubble

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

† The terminal velocity is v = g∆ρ D 2


D
t
18µ
† Simplification:
3πD 2 p 0 d 4D12 g∆ρD 2
6RT dt
( 2
)
(D ) = − πD C10
πD 18µ

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

† Thus given the velocity as a function of time, we can


calculate the distance traveled by the bubble by applying
the classical mechanics

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

† the distance that the bubble has traveled is


1 g∆ρ 5 / 2
H= D0
5γ 18µ

⎛ 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

† Nonporous catalyst: Simple


„ Nice simple geometry
„ No problem with mass transfer

† So why don’t we use non-porous catalysts?


Diffusion and Reaction in a Porous
Catalyst (2)
† Porous Catalysts vs non-porous catalysts

Porous Catalysts Non-porous Catalysts


High surface area Very low surface area per
unit mass
Low pressure drop High pressure drop
Easy to handle Difficult to handle

† This is why most catalysts used in


industries are porous!
Diffusion and Reaction in a Porous
Catalyst (3)
† So how do we model diffusion and reaction in a catalyst?
„ Should we model as detailed as possible? For example, we consider
every possible pores within a solid, assuming of course that we know
in details the connectivity between all pores.
Diffusion and Reaction in a Porous
Catalyst (4)
† So how do we model diffusion and reaction in a catalyst?
„ Or we shall model the catalyst particle as if it is homogeneous, and
take advantage of all that we know about the macroscopic properties
of the solid, for example
† Pore size
† Effective diffusivity
† Particle Porosity
† Particle tortuosity factor
† Specific surface area
† Shape of the particle
Diffusion and Reaction in a Porous
Catalyst (5)
† Pore size:
„ Pore size distribution: Choose the appropriate average pore size
† Effective diffusivity
„ So much has been done in 60 and 70.
† Particle Porosity
† Particle tortuosity factor
„ Pore is not straight
† Specific surface area; quite high 100-1000 m2/g
† Shape of the particle:
„ Make it simple
Diffusion and Reaction in a Porous
Catalyst (6)
† Two ingredients required to model diffusion and reaction in a catalyst
„ Diffusion flux
„ Reaction rate

† The diffusion flux done so far is for homogeneous media. For


heterogeneous media, like a porous catalyst, the molar flux could be
defined in the way as the Fick’s law
∂C ⎡ moles transported ⎤
J = −D eff ⎢⎣ total cross sectional area - time ⎥⎦
∂r
„ where the effective diffusivity is a function of system parameters as well as
the concentration
„ This form is identical to the heat flux equation for heterogeneous media
dealt with earlier
Diffusion and Reaction in a Porous
Catalyst (7)
† Equation for diffusion flux † Equation for heat flux

∂C ∂T
J = −D eff q = −k eff
∂r ∂r

„ The effective diffusivity is a „ The effective thermal


function of binary diffusivity, conductivity is a function of
the Knudsen diffusivity, the thermal conductivities of the
porosity and the tortuosity phases constituting the media,
and the porosity.

D eff = f (D12 , D K , ε, τ ) k eff = f (k f , k s , ε )


Diffusion and Reaction in a Porous
Catalyst (8)
† Equation for diffusion flux
∂C
J = −D eff
∂r

„ The effective diffusivity is a function of binary diffusivity, the Knudsen


diffusivity, the porosity and the tortuosity

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

2r 8R g T r = Pore radius (not particle radius)


DK =
3 πM M = Molecular weight
Diffusion and Reaction in a Porous
Catalyst (10)
ε
† The effective diffusivity D eff = Dc
τ
† The combined diffusivity is given by:
1 1 1
= +
D eff ,1 D12 D K ,1

† 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

† The pore size, pressure and temperature dependence

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 ⎥⎦

„ Let us deal with first-order reaction:

⎡ 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 ⎥⎦

† These are all we need to model diffusion and reaction in a


porous catalysts
Diffusion and Reaction in a Porous
Catalyst (15)
† Shell balance
⎛ Rate of ⎞ ⎛ Rate of ⎞ ⎛ Rate of mass⎞ ∆r
⎜ ⎟ −⎜ ⎟ +⎜ ⎟ = ( Accummulation)
⎝ mass in ⎠ ⎝ mass out⎠ ⎝ production ⎠

[( )
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

† But the diffusion flux is


∂C
N = − D eff
∂r r
† The final mass balance equation in terms
of concentration is then
D eff ∂ ⎛ 2 ∂C ⎞
⎜r ⎟ − ρ pSg kC = 0
r ∂r ⎝ ∂r ⎠
2

† This is now known as the classical


equation for diffusion and reaction in a
porous catalyst
Diffusion and Reaction in a Porous
∆r
Catalyst (17)
† So, the mass balance equation
D eff ∂ ⎛ 2 ∂C ⎞
⎜r ⎟ − ρ pSg kC = 0 r
r ∂r ⎝ ∂r ⎠
2

† The boundary conditions are:


∂C
r = 0; =0
∂r
r = R; C = C 0 (known bulk concentration )

„ 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 ⎟

† Since every term in the above equation is non-


dimensional, the group in the bracket MUST be
non-dimensional as well. We define that group as
ρ p Sg k R 2
φ2 =
D eff
„ This non-dimensional group is known as
† Thiele modulus in Western literature
† Damkohler number in German literature
† Zel’dowitch number in the Russian literature
Diffusion and Reaction in a Porous
∆r
Catalyst (21)
† So the mass balance equation is …..
1 ∂ ⎡ 2 ∂y ⎤ 2
x − φ y = 0 r
x ∂x ⎢⎣ ∂x ⎥⎦
2

† The physical significance of the Thiele modulus


⎛ R2 ⎞
⎜⎜ ⎟⎟
ρ p Sg k R 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

† Solution of this equation is u = Aeφx + Be − φx


Diffusion and Reaction in a Porous
Catalyst (24)
† Solution (continued)
u = Aeφx + Be − φx
„ The constants A and B can be found from the two boundary conditions
∂C ∂y
r = 0; =0 x = 0; =0 x = 0; u=0
∂r ∂x

r = R; C = C0 x = 1; y =1 x = 1; u =1

† Application of the two boundary conditions


1
x = 0; u=0 0=A+B A=
e φ − e −φ
1
x = 1; u =1 1 = Aeφ + Be − φ B=−
e φ − e −φ
Diffusion and Reaction in a Porous
∆r
Catalyst (25)
† So the solution for u is
r
e φx − e − φx sinh (φx )
u = φ −φ =
e −e sinh (φ)
u
† Since y=
x
† The solution for the non-dimensional concentration is
1 sinh (φx )
y=
x sinh (φ)
Diffusion and Reaction in a Porous ∆r

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 ⎣ ⎦

† Therefore the reaction rate per particle is


⎛ ∂C ⎞ ⎡ moles reacted ⎤
( )
W = 4πR 2 ⎜⎜ − D eff ⎟⎟
∂r r = R ⎠ ⎢ particle - time ⎥
⎝ ⎣ ⎦
Diffusion and Reaction in a Porous ∆r

Catalyst (27)
† Reaction rate per particle r

⎛ ∂C ⎞ ⎡ moles reacted ⎤
( ⎜ )
W = 4πR ⎜ − D eff
2
⎟⎟
∂r r = R ⎠ ⎢ particle - time ⎥
⎝ ⎣ ⎦

† Let put the RHS into non-dimensional form:


1 sinh (φx )
⎛ ∂ (C 0 y ) ⎞⎟ y=
( 2
⎜ )
W = 4πR ⎜ − D eff
∂ (Rx ) x =1 ⎟⎠
x sinh (φ)

dy 1 ⎡ φ cosh (φx ) sinh (φx )⎤
⎛ ∂y ⎞ = ⎢ −
W = −(4πRD eff C 0 )⎜⎜ ⎟⎟ dx sinh (φ) ⎣ x x 2 ⎥⎦
⎝ ∂x x =1 ⎠

This is your reaction rate per


W = −(4πRD eff C 0 )(φ coth φ − 1) particle written in terms of the
bulk concentration and the system
parameters
Diffusion and Reaction in a Porous ∆r

Catalyst (28)
† The reaction rate per particle is r

W = −(4πRD eff C 0 )(φ coth φ − 1)

† For very slow reaction compared to diffusion, φ << 1


1 φ
coth φ ≈ + +L
φ 3
⎛ 4πR 3 ⎞
W = −⎜⎜ ⎟⎟ρ pSg k C 0
⎝ 3 ⎠
„ The reaction is kinetically-controlled
Diffusion and Reaction in a Porous ∆r

Catalyst (29)
† The reaction rate per particle is r

W = −(4πRD eff C 0 )(φ coth φ − 1)

† For very fast reaction compared to diffusion, φ >> 1


coth φ ≈ 1

(
W = − 4πR 2 )( )
ρ pSg D eff k C 0

„ The reaction is diffusion-controlled


Diffusion through a Polymer Film (1)
† Type of membranes
„ Porous membrane:
† Pore sizes usually between 200 to 3000 nm. Transport through this type is
by viscous flow. Separation is due to size
„ Non-porous membrane
† The transport through this type of membrane is controlled by diffusion of
adsorbed molecules inside the membrane. The diffusivity is called the
intra-membrane diffusivity.
† The flux equation mimics the Fick’s law
dC
J = −D
dx
„ This intra-membrane diffusivity must be determined from experiments. With
the exception of very low concentration, this diffusivity is generally a
complex function of concentration and its gradient

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

Maintained at constant pressure, P0


Diffusion through a Polymer Film (4)
† The time lag method

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

† The solution is:


C x 2 ∞ sin (nπx / L ) ⎛ n 2 π2 D ⎞
= 1− − ∑ exp⎜⎜ − t ⎟⎟
H P0 L π n =1 n ⎝ L 2

Diffusion through a Polymer Film (5)
† To determine the pressure change in the bottom
chamber, we have to set up the mass balance
around that chamber
d ⎛ PV ⎞ ∂C
⎜ ⎟ = −A D
dt ⎝ RT ⎠ ∂x x = L
t = 0; P=0
† Given
C x 2 ∞ sin (nπx / L ) ⎛ n 2 π2 D ⎞
= 1− − ∑ exp⎜⎜ − t ⎟⎟
H P0 L π n =1 n ⎝ L 2

† the pressure in 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
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

† At sufficiently large time, this solution has an


asymptote
A R T P0 H D ⎛ L2 ⎞
P= ⎜⎜ t − ⎟⎟
VL ⎝ 6 D ⎠
P

time