SEPARATION PROCESSES 1

Molecular Diffusion in Liquids

Dr.
FLUX EQUATIONS:
• The molar fux of component A in a binary mixture is given by
Ficks Law,

• The equation is valid for both gas and liquid phases.

• Unlike ideal gases, total molar concentration of a liquid
varies
from one point to another therefore average total molar
concentration is used. Put ,
DIFFUSION OF A THROUGH NON DIFFUSING B:

• NB = 0,
DIFFUSION OF A THROUGH NON DIFFUSING B:
EQUIMOLAR COUNTER DIFFUSION OF A AND B:

• NA = -NB,

• By integration,
EXPERIMENTAL DETERMINATION OF LIQUID PHASE
DIFFUSION COEFFICIENT:

• Thediaphragm cell consists of two compartments separated by

a porous diaphragm made of sintered glass.
• Solutions
of specie A in solvent B are taken at two different
concentrations in the two compartments.
EXPERIMENTAL DETERMINATION OF LIQUID PHASE
DIFFUSION COEFFICIENT:

• Diffusion occurs across the pores from higher concentration cell

to lower concentration cell.
• The contents of the compartments are kept well stirred.
• At the end of the run, samples are taken from the cells and
analyzed for the concentration of A.
• Effective area avaialble for diffusion = aε
• a = cross section area of diaphragm
• ε = porosity
• The length of diffusion path is not equal
to the thickness of
diaphragm because the pores are not straight and are
interconnected and some may have dead ends.
EXPERIMENTAL DETERMINATION OF LIQUID PHASE
DIFFUSION COEFFICIENT:

• Therefore an empirical parameter tortuosity factor is

introduced.

• For diffusion in liquid phase, at very low concentration the bulk

flow term is neglected.

• By integrating,
EXPERIMENTAL DETERMINATION OF LIQUID PHASE
DIFFUSION COEFFICIENT:

• l = Thickness of the diaphragm,

• lτ = Effective length of diffusion path
• If V1 and V2 are the volumes of the solutions in the two cells and
CA1 and CA2 are the concentration,

• By adding above equations and putting the value of NA,

EXPERIMENTAL DETERMINATION OF LIQUID PHASE
DIFFUSION COEFFICIENT:

• Cell Constant
PROBLEM:
*0
PREDICTIVE EQUATIONS FOR LIQUID PHASE DIFFUSION:

• The magnitude of liquid phase diffusivity is much smaller than

that of gas diffusivity.
• Values for different liquid mixtures can be found in literature.
PREDICTIVE EQUATIONS FOR LIQUID PHASE DIFFUSION:

• Correlations and semi empirical equations are available for the

prediction of liquid phase diffusivity but accuracy is not as good
as in case of gases.
• Wilke-Chang Equation:
PREDICTIVE EQUATIONS FOR LIQUID PHASE DIFFUSION:

From Wilke-Chang Equation, it is interpreted,

• Diffusivity
varies linearly with the absolute temperature and
inversely with the viscosity of the medium.
• Stokes-Einstein equation show this kind of dependence

• Larger molecules have lower diffusivities.

KNUDSEN DIFFUSION, SURFACE DIFFUSION & SELF
DIFFUSION:
KNUDSEN DIFFUSION:
• When the molecular mean free path is much larger than the
diameter of the pore in which the diffusing molecules reside, the
molecules collide with the wall rather than colliding with other
molecules. This mode of transport is known as knudsen diffusion.
• The mechanism is important when pore size is below 50 nm such
as transport in a catalyst containing fine pores.
• Based on kinetic theory of gases, Knudsen diffusivity is given by
KNUDSEN DIFFUSION:
• Equation can be reduced to

• Flux due to Knudsen diffusion is given by

PROBLEM:

Here Á is Angstrom which is equal to 0.1nm

SURFACE DIFFUSION:
• Transport of adsorbed molecules on a solid surface in the
presence of a concentration gradient on the active sites is called
as surface diffusion.
• Flux due to surface diffusion is given by

• The experimental values of Ds range between 10-4 – 10-5 cm2/s.

SELF DIFFUSION:
• The diffusion of molecules in a pure substance.
• Molecules of a gas or liquid move continuously from one position
to another position.
• The corresponding diffusion coefficient is called as self
diffusivity or self diffusion coefficient.