Lecture 2

Understand the origins and meaning of Ficks first law. Understand the concepts of mass transfer velocity, equimolar counter diffusion and unimolar diffusion. Understand how to estimate diffusion coefficients. Reading: Chapter 3

Ficks First Law of Diffusion

Ficks first law of diffusion (fundamental or mechanistic):
Diffusion is a spontaneous phenomenon when a system contains two or more components whose concentrations vary from point to point, there is a natural tendency of mass to be transferred in the direction that eliminates (or minimises) concentration differences within that system:

JA,z = DAB

dc A dz
Adolf Eugen Fick (1829-1901)

This is an extension of Thomas Graham's work his law states that the rate of effusion of a gas is inversely proportional to the square root of its molar mass.

What is mass transport by diffusion?

For an active diffusion to occur, the temperature should be high enough to overcome energy barriers to atomic motion.

http://people.virginia.edu/~lz2n/mse209/Chapter5.pdf

Fundamentals of Mass Transfer and Diffusion Fickian Diffusion

Lets consider a unit volume that contains a mixture of n different components and write the following definitions:
Mass concentration (density): Mass fraction of component A:
Where

(1) (2)

Total molar concentration:

(3)

Molar concentration of comp. A:

(4)

Mole fractions (e.g., component A) :

In liquids (or solids): xA=CA/C In gases: yA=CA/C

Fundamentals of Mass Transfer and Diffusion Flux Ficks Law In terms of the mass diffusion flux in one dimension, we can write (for constant density):

We can also write these same equations for all spatial dimensions (assuming.?):

Fundamentals of Mass Transfer and Diffusion Flux Ficks Law

What is important is to differentiate the diffusion of species i from the movement the same species due to bulk movement (e.g. flow in a pipe).

Ni = xiN + Diffusion Flux

(0)

Fundamentals of Mass Transfer and Diffusion Velocities Can define the molar average velocity as the total molar flux, N, divided by the total molar concentration, c: N NA + NB vm = = (1) c c For species i":
Combine these 2:

Ni vi = ci
vm = x A v A + xB vB

(2)

(3)

Fundamentals of Mass Transfer and Diffusion Velocities Now, do the same thing, but just with the diffusion flux to get the species average diffusion velocity:
(4)

Ji vi,D = = vi vm ci

vi = vm + vi,D

Ni Substitute: vi = ci

Ni = ci vm + ci vi,D

dx A ) For a binary system: NA = x AN cDAB ( dz

Fundamentals of Mass Transfer and Diffusion In our binary system we have:

dx A NA = x AN cDAB ( ) dz

and by analogy
dxB NB = xBN cDBA ( ) dz

Fundamentals of Mass Transfer and Diffusion Binary diffusion limiting cases

From our flux equations, it can be seen that there are two limiting cases that describe mass transfer by diffusion:
Equimolar counter diffusion: fluxes are equal, but opposite in direction. Unimolecular diffusion: one component diffuses through a quiescent 2nd component.

Fundamentals of Mass Transfer and Diffusion Steady State Equimolar Counter Diffusion
Flux of one gaseous component is equal to but in the opposite direction of the second gaseous component
z1 A z2

N = NA,z + NB,z = 0

For steady-state, no reaction, in the zdirection:

d NA,z = 0 dz

the molar flux is

dx A NA,z = cDAB + x A (NA,z + NB,z ) dz

Fundamentals of Mass Transfer and Diffusion Steady State Equimolar Counter Diffusion In equimolar counterdiffusion, NA,z = -NB,z

Integrated at z = z1, cA = cA1 and at z = z2, cA = cA2 to:

DAB NA,z = (c A 1 c A 2 ) (z 2 z1 )

Or in terms of partial pressure, DAB NA,z = (p A1 p A 2 ) RT(z 2 z1 )

Fundamentals of Mass Transfer and Diffusion Steady State Equimolar Counter Diffusion
The concentration profile is described by d

d2c A NA,z = =0 2 dz dz

Integrated twice with boundary conditions at z = z1, cA = cA1and at z = z2, cA = cA2 to yields a linear concentration profile: c c zz
A A1

c A1 c A 2

z1 z 2

Fundamentals of Mass Transfer and Diffusion Steady State Unimolecular Diffusion

Flux of one gaseous component is non-zero, the other flux is negligible.

dx A the molar flux of A is NA,z = cD AB + x ANA,z dz

cDAB dx A NA,z = (1 x A ) dz

Fundamentals of Mass Transfer and Diffusion Steady State Unimolecular Diffusion Rearrange and integrate flux of A:
cDAB 1 x A NA,z = ln (z z1 ) 1 x A1
cDAB dx A dz = N (1 x ) A , z X A ,1 A z1
z xA

NA (z z1 ) x A = 1 (1 x A1 )exp cDAB

Detailed in Seader and Henley page 70. Work through examples 3.1 and 3.2 and the tutorial of this week.

Fundamentals of Mass Transfer and Diffusion Gas Phase Diffusion Coefficients (section 3.2) Have been treating D as a known parameter. It is relatively complex:

Huge range of values.

Gases 10-1 cm2/s Liquids 10-5 cm2/s Polymers and Glass 10-8 cm2/s Solids 10-30 cm2/s

Fundamentals of Mass Transfer and Diffusion Gas Phase Diffusion Coefficients Calculating diffusion coefficients from first principles is easier for gases than liquids.
Based on Boltzmans kinetic theory of gases, theorem of corresponding states and a suitable description of intermolecular energy potential function (Lennard-Jones potential)

In gases diffusivity proportional to the average molecular velocity times the mean free path (distance travelled until collision):

Gas Phase Diffusion Coeff.

Why so much higher?

Fundamentals of Mass Transfer and Diffusion Gas Phase Diffusion Coefficients Chapman Enskog

Rigorous extensions using molecular sizes, Lennard-Jones interaction potentials etc, lead to Chapman-Enskog equation:
[=] K

[=]

cm2/s

[=] atm Effective collision diameter ()

Collision Integral Tabulated as a function of kBT/AB AB = (AB)0.5

AB = (A+ B)/2

N.B. This is just one possible equation. There are many other models for calculating DAB, but they all use essentially the same parameters.

Fundamentals of Mass Transfer and Diffusion Gas Phase Diffusion Coefficients

Fundamentals of Mass Transfer and Diffusion Gas Phase Diffusion Coefficients

Example: Calculate the diffusivity of benzene in air at 100C and 2 atm (a) using Chapman-Enskog and (b) by extrapolation from tabulated value at 1 atm and 0C.
(a) From our tables (previous page): Air /k 78.6 3.711 M 78.1 29 Benzene 412.3 5.349

Fundamentals of Mass Transfer and Diffusion Gas Phase Diffusion Coefficients Example continued
(b) From our tables (previous page) at 0C and 1 atm: DAB=0.299 ft2/h = 0.0772 cm2/s

Fundamentals of Mass Transfer and Diffusion Diffusion in Small Pores

When diffusion occurs in small pores, and pore diameter is less than mean free path, physical constraints of the pores will influence the rate of diffusion. This is know as Knudsen diffusion. For a cylindrical pore (T in K; M = mol wt; r = radius in cm; D[=]cm2/s):

For general pore size:

Fundamentals of Mass Transfer and Diffusion Liquid Phase Diffusion Coefficients The theory of diffusion for liquid phase systems is not nearly as advanced as for gas phase. DAB for liquids 104-105timessmallerthatforgas.
Meanfreepathmuchsmaller(typicallylessthana moleculardiameter). Muchgreaterdensitiesmeansthatfluxisroughlythe sameorderofmagnitude.

Forlargesphericalmoleculesinverydilute solutions,Stokes-Einsteinequationgives:
Viscosity

Molecular radius

Fundamentals of Mass Transfer and Diffusion Liquid Phase Diffusion Coefficients

The S-E equation gives functionality, but underestimates real diffusivities (because the drag on the molecules is less than postulated by S-E):
S-E says D varies as V- (i.e. r-1) In reality D varies as V-0.6

Another empirical expression is the Wilke-Chang (for small molecules):

B = 2.6 for water = 1.9 for methanol = 1.5 for ethanol = 1 for benzene = 1 for heptane

Fundamentals of Mass Transfer and Diffusion Liquid Phase Diffusion Coefficients Example: Find the diffusivity of toluene in benzene and benzene in toluene at 110C. The physical properties are:
MW Benzene Toluene 78.1 92.1 TNBP 80.1 110.6 VA 96.5 118.3 at 110C 0.24 0.26