Membrane Transport Theory
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Transport Theory
Two models:
1. Pore-flow model
2. Solution diffusion model
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Transport Theory
Pore-flow model
The most important property of membranes
is their ability to control the rate of Rejected
permeation of different species.
Permeate
The pore-flow model (right side), in which
permeants are transported by pressure-
driven convective flow through tiny pores.
Separation occurs because one of the
permeants is excluded (filtered) from some
of the pores in the membrane through which
other permeants move.
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Transport Theory
Darcy’s Law
Pressure-driven convective flow, the basis of
Darcy’s law
the pore-flow model.
Commonly used to describe flow in a capillary
or porous medium.
dp/dx is the pressure gradient existing in the
porous medium, ci is the concentration of
component i in the medium, and K’ is a
- Permeant travels
coefficient reflecting the nature of the medium.
through the pores
In general, pore-flow pressure-driven - Higher flux relative to
membrane fluxes are high compared with diffusion model
those obtained by simple diffusion.
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Pore-flow membranes
Ultrafiltration and microfiltration Membranes
Characterized by large pores and an open
structure- Follow Darcy’s law
Contaminant size matters
Right side-SEM images of the different
membranes with various porosities (prepared
in different methods)
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Pore-flow membranes
Ultrafiltration and microfiltration
membranes used to filter particulates
from water or liquids.
The membrane porosity (ε) is the
fraction of the total membrane volume
that is porous.
Membrane tortuosity (τ) describes how
twisted the pores are compared to the
membrane [Link] pores are
straight and go directly through the
membrane, τ = 1, because the pore
length equals the membrane
[Link] real membranes, pores
usually bend and twist, so the pore
path is longer, giving typical τ values
between 1.5 and 2.5.
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Transport Theory
Solution-diffusion model
Permeants dissolve in the membrane material
and then diffuse through the membrane down
a concentration gradient.
Permeants are separated because of
differences in their solubilities in the
membrane and differences in the rates at
which they diffuse through the membrane.
The most common model used nowadays
Example: Human Barrier/size vs connections
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Transport Theory
Fick’s Law
Molecules will move from the high- Fick’s law of diffusion (1855)
concentration to the lower-concentration side.
This is associated with the solution-diffusion
model.
Where Ji is the rate of transfer of component i
or flux (g/cm2·s) and dci /dx is the - Diffusion is a slow process
concentration gradient of component i - To increase membrane flux, very
thin layers were used
(g/cm3·cm).
The term Di is called the diffusion coefficient High concentration
Requires shorter time
(cm2·s) and measures the mobility of
Requires longer time
individual molecules.
The minus sign indicates that diffusion
proceeds down the concentration gradient
(from high to low). Thinner is faster
Low concentration
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Transport Theory
Fick’s vs Darcy’s Law
In solution-diffusion membranes, pores are
tiny, temporary free-volume spaces that
appear and disappear with polymer motion, so
transport follows Fick’s law.
In pore-flow membranes, pores are large,
permanent, and interconnected, remaining
stable during permeant movement, so v v
transport follows Darcy’s law.
Larger, long-lasting pores increase the
likelihood that a membrane behaves according
to the pore-flow mechanism.
The transition between transient (solution-
diffusion) and permanent (pore-flow) pores is
a diameter in the range of 5–10 Å.
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The Solution-Diffusion Model
Applies to reverse osmosis, pervaporation,
and gas permeation in polymer films.
It involves the diffusion of molecules within a
dense polymer (although the above process
differs in many ways).
Similar membranes can be used in very
different processes.
Cellulose acetate membranes were developed
for reverse osmosis and are also used in
pervaporation and gas separation.
MD simulation for the CO2 molecule moving
between polymer chains (right side).
6FDA-4PDA polymer matrix
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The Solution-Diffusion Model
Molecular dimensions of gases Simulated trajectories of helium, oxygen, and
methane molecules during a 200-ps
time period in a poly(dimethylsiloxane) matri
Shape and size affects the diffusion
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Application of the Solution-Diffusion Model
Dialysis a) b) c)
Reverse Osmosis
Gas Separation
Pervaporation
a) Water moves from a place with
more water to a place with less
water (fresh to salty)
b) Osmotic equilibrium is the point where
water stops moving across a
semipermeable membrane.
c) RO is opposite to the normal osmosis.
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Transport Theory
200 500
Pore size determination
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The average pore diameter in a
membrane is difficult to measure
directly and must often be inferred
from the sizes of molecules that
permeate it or by other indirect
techniques.
Known Mw for each molecule can Wet-Saturated Dry membrane
Pores filled with liquid
give an indication of the porosity.
Example: molecules with Mw of Fluid
100, 200, 300, and 400 pass, while Gas pressure
molecules with 500 do not. applied
Other methods, such as a
porometer, can be used to Smaller pores require higher pressure
measure the pore size.
As P increase, gas replace liquids, starting from large poresv
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Permeation in Ultrafiltration and Microfiltration Membranes
Screen filtration Depth filtration
• These membranes contain • Particles to be removed inside
surface pores smaller than the the membrane.
particles to be removed. • Particles are captured by smaller
• Particles are captured at the pores inside or by adsorption.
surface of the membrane. • Mostly for microfiltration
• Anisotropic membranes, fine membranes
microporous surface layer
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Permeation in Gas separation Membranes
Microporous membranes with a dense
structure
Gas permeability depends on solubility and
diffusivity
Solubility includes interaction between
membranes and gases
Diffusivity focuses on the gas size and size-
sieving properties of the membranes
P= DxS (Barrer)
Further details on gas separation will be
provided in separate sessions during this
course.
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