Osmosis , Electro-osmosis

and Diffusion
Tahir Khalid
Trainee Chemical Engineer
Osmosis: Osmosis is the movement of solvent particles across a
semipermeable membrane from a dilute solution into a concentrated
solution. The solvent moves to dilute the concentrated solution and
equalize the concentration on both sides of the membrane.
Diffusion: Diffusion is the movement of particles from an area of higher
concentration to lower concentration. The overall effect is to equalize
concentration throughout the medium.
Examples
• Examples of Osmosis: Examples include red blood cells swelling up
when exposed to freshwater and plant root hairs taking up water. To
see an easy demonstration of osmosis, soak gummy candies in water.
The gel of the candies acts as a semipermeable membrane.
• Examples of Diffusion: Examples of diffusion include the scent of
perfume filling a whole room and the movement of small molecules
across a cell membrane. One of the simplest demonstrations of
diffusion is adding a drop of food coloring to water. Although other
transport processes do occur, diffusion is the key player.
Similarities
Osmosis and diffusion are related processes that display similarities:
• Diffusion and osmosis are both passive transport processes that act to
equalize the concentration of a solution.
• In diffusion, particles move from an area of higher concentration to
one of lower concentration until equilibrium is reached. In osmosis, a
semipermeable membrane is present, so only the solvent molecules
are free to move to equalize concentration.
Difference B/w Osmosis and Diffusion
• One big difference between osmosis and diffusion is that both solvent and
solute particles are free to move in diffusion, but in osmosis, only the
solvent molecules (water molecules) cross the membrane. This can be
confusing because while the solvent particles are moving from higher to
lower solvent concentration across the membrane, they are moving from
lower to higher solute concentration, or from a more dilute solution to a
region of more concentrated solution. This occurs naturally because the
system seeks balance or equilibrium. If the solute particles can't cross a
barrier, the only way to equalize concentration on both sides of the
membrane is for the solvent particles to move in. You can consider osmosis
to be a special case of diffusion in which diffusion occurs across a
semipermeable membrane and only the water or other solvent moves.
Electro- Osmosis
• The charged colloidal particles move under the influence of an electric
field during electrophoresis. If electrophoresis is avoided by
maintaining the particles stationary, the dispersion medium will move
under the influence of an electric field. This movement of dispersion
medium under the influence of an electric field is called electro-
osmosis.
• If colloidal particles carry negative charge, the diffused layer has a
resultant positive charge. Therefore, the dispersion medium will move
towards negative electrode and if the particles are positively charged,
the dispersion medium will move towards positive electrode since it
has now resultant negative charge.
•  In this method, the electroosmosis pressure is related to zeta
potential by the equation
•ζ=
• where, P = electroosmosis pressure in Nm2 ; r = radius of the capillary
in cm; E = applied potential in e.s.u. and D = dielectric constant of the
medium.
• The properties of liquid
• The applied potential
Diffusion
• Spontaneous movement of molecules due to concentration gradient
is called Diffusion or Mass transport by atomic motion, Diffusion is a
consequence of the constant thermal motion of atoms, molecules
and particles that results in material moving from areas of high to low
concentration
• Diffusion is defined by first ficks law which relates mass flux of a
component to its composition gradient employing a constant of
proportionality called diffusivity as,
• Ja= -Dab dCa/dz
Diffusion through Nafion Membrane
• Diffusion results from the concentration gradient dC/dx in the
medium and hence, occurs when the NaCl concentration in the anode
compartment differs from that in the cathode compartment. In a
chloralkali cell,the anolyte is nearly a saturated NaCl solution,where
as the catholyte contains only traces of NaCl.Although Cl~ion is
subjected to the same diffusional driving force as Na"^ion,it is
rejected by the fixed anions in the membrane,which also retard the
transport of Na“ to some degree to maintain the charge balance.
• There are boundary layers at each side of the
membrane where the Na ion concentration differs
from the bulk concentration because of insufficient
mixing of the solution Figure above illustrates this
concept. C denotes the concentration,ζ the distance,
the subscripts A,C and m to the anolyte, catholyte,and
the membrane respectively, and refer to the solution
membrane interfaces.Omitting the subscript
• Na,the diffusional flux is given as:
Mass Transfer across membrane
• The mass transport of anions across a membrane is governed by
diffusion, migration,and electro osmotic water convection and can be
described using the Nernst-Planck equation.
• N = -D.dC/dx – zF/RT . DC.dø/dx + Cv (1)
Where N = flux of species,
D = diffusion coefficient
dC/dx= concentration gradient
dø/dx = potential gradient
z =charge of specie
F=faraday constant
C=concentration of species
v = electro-osmotic water velocity
Cont…
• The voltage gradient, dø/dx,is related to the current density,i (Acm-
2
),and membrane conductivity , k{ohm-1cm-1),by:
• dø/dx=-i/k (2)
• SubstitutingEq.(2) into (1) gives:
N = -D.dC/dx + zF/RT . DC.i/k + C v
= -D.dC/dx + C(zF/RT.D.i/k + v )
u = - zDFi/RTk
So,
N = -D.dC/dx – C( u - v)_________
• It follows from that anions such as Chlorite and chlorate ,present at high
concentrations in the anolyte,are transported to the cathode compartment by
diffusion
• And due electroosmotic flow repelled by the potential gradient. We can now
examine the
• Effect of current density,anolyte chloride and chlorate concentration,and the
anolyte
• Temperature on the extent of transport of these anions into the cathode
chamber,based
• On the transport characteristics of a given membrane.
• Unfortunately,all the properties required for the calculations are not available
• In the open literature for the membranes that are used commercially. Therefore
some
• Simplified descriptions and assumptions are employed here to show the trends
expected of a membrane under given operating conditions.
Effect of impurities
pH Effect
Effect of nonionic impurities
Cont…
Cont…