BINARY DIFFUSION COEFFICIENTS

Gases
y Magnitude } 101 cm2 / s y Temperature dependence: y Weak dependence on concentration y Pressure dependence: } p 1 Experimental determination of diffusivities method developed by Winkelmann - liquid is allowed to evaporate in a vertical glass tube over the top of which a stream of vapour-free gas is passed, at a rate such that the vapour pressure is maintained almost at zero.

apparatus is maintained at a steady temperature no eddy currents in the vertical tube and mass transfer takes place from the surface by molecular diffusion alone. evaporation rate determined by fall of liquid surface conc known - diffusivity calculated. calculate the diffusivity of carbon tetrachloride vapour in air at 321 K and atmospheric pressure Time from Liquid Time from Liquid commencement level commencement level of experiment of experiment h min ks mm h min ks mm 0 0 0.0 0.0 32 38 117.5 54.7 0 26 1.6 2.5 46 50 168.6 67.0 3 5 11.1 12.9 55 25 199.7 73.8 7 38 27.4 23.2 80 22 289.3 90.3 22 16 80.2 43.9 106 25 383.1 104.8 The vapour pressure of carbon tetrachloride at 321 K is 37.6 kN/m2 and the density of the liquid is 1540 kg/m3. The kilogram molecular volume may be taken as 22.4 m3.

Diffusion Coefficient for Gases Prediction

two approaches: 1. The kinetic theory of gases 2. Use of molecular interactions Simple Kinetic Theory dilute gas mixtures at low pressures molecules are rigid, non-attracting, and spherical. rigid spherical particles and elastic collisions = average velocity of molecules = mean free path Lennard-Jones Accounting for intermolecular forces and different sizes of the two component molecules
1.8583 10 7 T 1 1 2 ! + ( ) 2 PW AB ; D , AB MA MB
3 2 1

DAB

cm 2 s

T ! Temperature, M = Molecular weight, kg p = absolute pressure, atm

W AB = collision diameter , m ; D , AB ! collison int egral

kgmol

Fuller semi-empirical method

T ! Temperature, M ! Molecular weight , kg

3 v ! Diffusion volume, m

kgmol

kgmol

p ! total pressure, atm

from these eqns

Liquids
y Order of magnitude: s y Generally increasing function of temperature y Pressure insensitive y Often a strong function of concentration density and resistance to diffusion higher than in gases - intermolecular forces more important difficult to characterize theoretically - correlation of data and prediction difficult. Stokes-Einstein hydrodynamic model very large spherical molecule (A) diffusing in a liquid solvent (B) of small molecules
2 10 5 cm

viscosity in Pas solute molar volume at b.p. m3/(kg mol) VA

useful eqn for the calculation in of dilute solutions of non-electrolytes Wilke and Chang semi-theoretical dilute solution
DAB ! 1.173 v 1016 JM B
12

T 0.6 Q BVA

DAB diffusivity of solute A in solvent B (m2/s), association factor for the solvent (2.26 for water, 1.9 for methanol, 1.5 for ethanol and 1.0 for unassociated solvents such as hydrocarbons and ethers), MB molecular weight of the solvent, 2 B viscosity of B (N s/m ) T temperature (K), and VA molar volume of the solute (m3/kmol) - Values for simple molecules given in Table. For more complex molecules, VA calculated by summation of the atomic volume and other contributions for water 0.0756 m3/kmol should be used.

Solids
mechanism in crystalline solids - movement of atoms into vacancies or by interstitial movement.

2

Order of magnitude: quite variable 10 cm Strong temperature dependence } exp( B RT )

5

Porous Solids Diffusion through solids can be by three mechanisms: Ordinary diffusion Knudsen diffusion Surface diffusion When the pore diameter is large in comparison to the mean free path then ordinary diffusion occurs and in the contrary case Knudsen diffusion

occurs. In either case it can be accompanied by surface diffusion that occurs when molecules adsorbed on the surface move along the surface usually in the direction of decreasing concentration (actually, in general, decreasing chemical potential). Surface diffusion is the most difficult to characterize. In Knudsen diffusion the molecules collide more often with the pore wall than with other molecules and it can be predicted from kinetic theory: ud D ! . 3 Here u is the velocity of the molecules and d is the diameter of the pore. For straight, round pore:
0 A( K )

0 A( K )

T 2 ! 97 r ( ) MA

Here
r
m2 s

0 DA ( K )

= pore radius, m = Knudsen diffusion coefficient,

T = temperature, K The mean pore radius can be estimated by

r!

2V p 2I ! S VB S

. S = surface area of porous solid, m kg V = bulk density of solid, kg m V = specific pore volume, m kg I = porosity of solid
2

Here
B
3

In order to account for the tortuousity of the pores on can use: . Here X is the tortuousity factor, a measure of the deviation from straight cylindrical pores. Example T(K)
X I
I 0 0 D A( K ) ! D A( K ) ( ) X

r(m)

1. Silica-alumina 0.725 0.40 catalyst

298

1.6 10 9