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D. D. Do

University of Queensland

Mode of Mass Transfer

Diffusion:

Molecular diffusion

Knudsen diffusion

Convection

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

n

∑C v

k =1

k k

Velocities and Average Velocities (2)

Different components move at different velocities

2 v2

1

v1

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

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

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

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 ⎠

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 *)

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

dx1

J 1 = − cD12

dz

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

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

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

“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 ⎠

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 ⎠

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 ⎠

⎛ 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 ⎟⎠

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 ⎟⎠

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

1

boundary condition as

cD12 ⎛ 1 − x 1,0 ⎞

K1 = ln⎜ ⎟

z 2 − z1 ⎝ 1 − x 1,L ⎠ 0

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 ⎟⎠

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 ⎠

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 ⎠

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 ⎠

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!!

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 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

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

transfer coefficient

Dissolution of a Sphere (6)

So the Sherwood number for a stagnant environment is

k m (2 R )

=2

D12

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

law equation

Diffusion with Heterogeneous n A → An

Reaction (3) A An

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

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

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

cD 12 dx 1

N1 = − ≡ −K1

⎡ (n − 1) ⎤ dz

A

⎢⎣1 − n x 1 ⎥⎦ An

⎡ 1 ⎤ ( n − 1)

cD 12 ln ⎢ ⎥= K1z + K 2

⎣ 1 − ( n − 1) x 1 / n ⎦ n

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

⎡ ⎤ ( 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

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

( 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:

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

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

cD 12 dx 1

N1 = − ≡ −K1

⎡ (n − 1) ⎤ dz

A

⎢⎣1 − n x 1 ⎥⎦ An

⎡ 1 ⎤ ( n − 1)

cD 12 ln ⎢ ⎥= K1z + K 2

⎣ 1 − ( n − 1) x 1 / n ⎦ n

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

⎡ 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

⎡ 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

⎡ 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 ⎠

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 ⎠

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 ⎠

non-dimensional group

⎛ kL ⎞ chemical reaction rate

⎜ ⎟≡

⎝ D 12 ⎠ diffusion rate

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

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

⎜ ⎟ −⎜ ⎟ +⎜ ⎟ = ( Accummulation)

⎝ mass in ⎠ ⎝ mass out⎠ ⎝ production ⎠

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

( )

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

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

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

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

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

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

⎜ ⎟ −⎜ ⎟ +⎜ ⎟ = ( 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

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

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

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 ⎠⎦

=− 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 ⎦

∂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

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

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

⎜⎜ ⎟⎟ = 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

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

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

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

Nice simple geometry

No problem with mass transfer

Diffusion and Reaction in a Porous

Catalyst (2)

Porous Catalysts vs 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

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

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

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.

Diffusion and Reaction in a Porous

Catalyst (8)

Equation for diffusion flux

∂C

J = −D eff

∂r

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

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

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 ⎥⎦

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

∂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

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

∂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 ⎟

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

⎛ 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

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

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 ⎣ ⎦

⎛ ∂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 ⎥

⎝ ⎣ ⎦

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 ⎠

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

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

coth φ ≈ 1

(

W = − 4πR 2 )( )

ρ pSg D eff k C 0

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

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

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

asymptote

A R T P0 H D ⎛ L2 ⎞

P= ⎜⎜ t − ⎟⎟

VL ⎝ 6 D ⎠

P

time

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