Membrane Separation

UNIT 11 MEMBRANE SEPARATION

Structure
11.1 Introduction
Objectives
11.2 General Aspects of Membrane Process
11.3 Some Important Membrane Processes
Reverse Osmosis (RO)
Nanofiltration (NF)
Ultrafiltration (UF)
Microfiltration (MF)
Dialysis
Electrodialysis (ED)
Gas Separation
Prevaporation
Liquid Membrane Processes
11.4 Mechanisms of Separations through Membranes
Sieving
Solution-Diffusion
Preferential Sorption-Capillary Flow
Donnon Effect
Knudsen Flow
Surface Flow
Facilitated Diffusional Transport
Active transport
11.5 Osmotic Phenomena
11.6 Reverse Osmosis Process
Basic Equations
Concentration Polarization
11.7 Dialysis
11.8 Electrodialysis
11.9 Applications
Desalination and Water Treatment
Protein Recovery
Production of Table Salt
Hemodialysis
Ion Selective Membrane Electrode
Specific Gas Probes
Detection and Analysis of Particulate Contamination
Microbiological Analysis
11.10 Summary
11.11 Terminal Questions
11.12 Answers

11.1 INTRODUCTION
In Unit 1 of this course, two types of classifications for different separation methods
were proposed–one based on the property leading to separation and the other on
equilibrium and rate processes. Membrane separations figure under the category of
molecular geometry in one (sub-Sec. 1.6.6) and in the rate processes under first (sub-
Sec. 1.7.2). Inclusion of membrane separations under these two classifications very
aptly defines the principles behind the membrane separations. Membrane processes
utilize semipermeable/ permselective membranes to achieve separations of various
chemical substances which can be either in solid, liquid or in gaseous forms.
Membrane processes can be used to separate chemical substances in various sizes
from microscopic to molecular level. For example, membranes can be used to separate

5
Other Separation suspended particles from a turbid solution, separation of dissolved solutes from saline
Methods waters, separation of toxic metabolic products from blood, separation of a gas from a
mixture of gases and so on.

The membrane separations are different from many of the other separation processes
like solvent extraction, chromatographic methods involving partition, adsorption, ion
exchange etc. which involve an equilibrium between the substances getting separated
and the separating phases. The onset of equilibrium in these process restricts the
extent of separation achievable and the equilibrium is shifted suitably to achieve the
desired level of purity. Also, in some of these processes, a reversal of equilibrium is
often necessary to regenerate the separating medium so that it can be reused. In these
processes which are equilibrium governed, we always talk of how much separation is
accomplished in terms of partition coefficients or distribution ratios.

In contrast, membrane processes are rate governed processes wherein we talk not only
of relative quantity of the substance separated but also about the rate at which the
separation is taking place. Also, membrane processes are continuous separation
processes and there is no need of membrane regeneration as is required in equilibrium
governed processes. Because of some of its inherent advantages, the membrane
processes are replacing some of the well known separation techniques for
technological applications.

The present unit is devoted to membrane separations. It starts with a simplified picture
of membrane separation, familiarity with some of the general terms and a
classification of different membrane processes. The important characteristics of these
processes are briefly discussed. This is followed by a description of the different
mechanisms of separation by membrane processes. The processes like osmotic
phenomena, reverse osmosis, dialysis and electrodialysis are explained in detail.
Membrane separations have multidisciplinary applications and some of these are
highlighted towards the end of the unit.

Objectives
After studying this Unit, you should be able to
• explain the general aspects and importance of various membrane processes,
• understand and explain the various mechanisms involved in membrane based
separations,
• define the terms like product flux, solute retention percentage, percent recovery,
membrane fouling and concentration polarization,
• explain osmosis, reverse osmosis, dialysis and electrodialysis processes and
how they differ from each other, and
• enumerate some of the important applications based on membrane separations
from different areas of science and technology.

11.2 GENERAL ASPECTS OF MEMBRANE PROCESS

Before we discuss the different types of processes, it will be necessary to get a clear
picture of a simple membrane process and be familiar with the general terms in usage.
It may be equally important to know the criteria which evaluate the process under
consideration.

A generalised and simplified schematic of membrane separation process is given in

Fig. 11.1.

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 Membrane Membrane Separation

Influent with substances Permeate depleted with

A and B either A or B

Concentrate enriched with either A or B

Fig. 11.1: A schematic representation of a simple membrane process

In membrane separation processes, two bulk phases are separated by a barrier which is
called the membrane. The membrane controls the passage of different chemical
substances through it which depends upon the nature of the chemical substances and
the membrane. This results in depletion of that substance in the permeate through the
membrane.

The membrane phase can either be nonporous, microporous, mesoporous or

o o
macroporous. By IUPAC classification, pores between 20 A and 500 A are called
o
mesoporous and pores larger than 500 A are called macropores. A membrane can also
either be a solid or a liquid. It can be a polymeric material, inorganic refractory
compound or a metal or their composites.

Permeation of chemical species through membranes is achieved by applying a driving

force across the membrane. This can be in the form of hydrostatic pressure difference,
temperature difference, concentration difference, partial pressure difference or
electrical potential gradient. Application of different types of driving forces as
mentioned above across various types of membranes gives a broad classification of
membrane separation processes. Accordingly, the mechanism by which chemical
species permeate depends on the type of membrane process. The permeation of
chemical species across the membrane is kinetically driven by the application of
mechanical, chemical or thermal work.

The performance of the membrane is defined in terms of two simple parameters, viz.
transmembrane flux and solute retention or solute selectivity. Transmembrane flux
or permeation rate is the volumetric or mass or molar flow rate of a fluid passing
through unit area of membrane surface per unit time. Transmembrane flux of any
species, i, is directly proportional to the driving force applied across the membrane
and is inversely proportional to the effective thickness of the membrane. If the driving
force is described in terms of hydrostatic pressure gradient (∆P) or partial pressure
difference (∆pi) or concentration difference (∆Ci ), across the membrane for any
species , i, then
J i = Pi ( ∆P or ∆pi or ∆Ci ) / δ … (11.1)
where, Ji is the transmembrane flux for species i, Pi is the permeability of species i,
through the membrane and is the effective membrane thickness.

The ratio of permeability of species i, to effective membrane thickness is sometimes

called permeance.

The retention or selectivity is a measure of the relative permeation rates of different

components through the membrane. It is often expressed as selectivity coefficient, α.

7
Other Separation For two species A and B permeating across a membrane, the selectivity coefficient for
Methods
species A with respect to B (α AB ) is given by as follows:

a BA = P A/ P B .... (11.2)
The selectivity coefficient can also be expressed as the ratio of concentration of the
two species in the permeate to the concentrate stream. Accordingly,
a BA = (CA / CB)p / (CA / CB )c ... (11.3)
where, CA and CB represent the concentration of species A and B, respectively and
the subscripts p and c represent the permeate and the concentrate, respectively.

11.3 SOME IMPORTANT MEMBRANE PROCESSES

The principal objective of a membrane separation process is separation of a desirable
substance from a given mixture. Today, almost all the membrane processes use
synthetic membranes. Although biological membranes carry out a number of
complicated separations in all life processes, they are not widely used. There are a
number of membrane processes which can be defined by considering the following
aspects:

• Separation objective–the nature of the substance which needs to be separated

from the nature of the mixture,
• The nature of the species retained by the membrane,
• The nature of the species permeating through the membranes,
• The driving force needed to achieve the desired separation, and
• The mechanism of separation.
There are several membrane separation processes which are of industrial importance
as on today. They are briefly discussed below with respect to their principal
characteristics.

11.3.1 Reverse Osmosis ( RO )

The Reverse Osmosis (RO) is a process wherein a relatively pure solvent is separated
from a salt solution by using a semipermeable membrane by the application of
hydrostatic pressure. The hydrostatic pressure can vary from 2 MPa to around 6 MPa
depending upon the salt content of the feed mixture. The solvent permeates
preferentially through the membranes whereas the solutes, particularly electrolytes
and low molecular weight nonelectrolytes are retained by the membranes. For
effectively retaining microsolutes having molecular weight less than 300 or effective
o
size less than 10 A , reverse osmosis process is used. The process is used to produce
relatively pure water or a concentrated solution of microsolutes from a given salt
solution.

A simple schematic of the process is given in Fig. 11.2. The most notable example of
reverse osmosis process is the production of drinking water from naturally occurring
saline waters. This process is discussed in more detail in subsequent sections of this
unit.

8
 Pressure in excess of Membrane Separation
osmotic pressure Semipermeable membrane

Solution

Pure water

Fig. 11.2: The schematic representation of a reverse osmosis process

11.3.2 Nanofiltration (NF)

The process of nanofiltration is slightly different from the reverse osmosis process in
the sense that the permeating species in this case is solvent as well as low molecular
solutes or low valency solutes. This process also operates with hydrostatic pressure
difference across a semipermeable membrane having pore sizes which are slightly
larger than that of reverse osmosis membranes. The pore sizes of NF membranes are
in the range of 10 -30 Å . The hydrostatic pressure used in this process can vary from
1.5 Mpa to 2 MPa. This process is essentially used to fractionate solutes based on
valency of either cation or anion and also to separate various organic solutes of low
molecular weights. Various applications of NF process are briefly outlined in latter
part of this unit.

11.3.3 Ultrafiltration (UF)

The ultrafiltration (UF) is a process wherein the solvent along with microsolutes
permeates through the membrane and macrosolutes are retained by the membranes.
This process is similar to sieving and the driving force is the hydrostatic pressure
across the membrane. The process is used to fractionate the solutes in a solution based
on their size or molecular weight difference. Size or the molecular weight difference
of the macrosolute retained by the membrane depends upon the pore size of the
membranes. Microsolutes whose effective sizes are smaller than the pore size of the
membranes permeate along with the solvent whereas macrosolutes whose effective
sizes are larger than the pore size of the membranes are retained. The driving force
used in ultrafiltration processes is of the order of 500 kPa or so. The membranes used
o o
in ultrafiltration processes have pore sizes ranging from around 30 A to about 200 A .
Typical applications of the ultrafiltration process are the concentration of protein in
milk for cheese making and separation of colloidal particles, oils and macromolecules
from effluent waters as well as from surface waters.

11.3.4 Microfiltration (MF)

The microfiltration (MF) is a process mainly used for the separation of submicron size
(< 0.1 µm) particulate matter from solution. This process also requires hydrostatic
pressure gradient across the membrane and the pressure used is of the order of 100
kPa or so. The pore size of the membranes decide the size of the particulate matter
retained. The process is similar to ultrafiltration and separation takes place by sieving.

The essential difference between ultrafiltration and microfiltration is the size of the
macrosolute retained, pore size of the membranes and the hydrostatic pressure needed
across the membranes. Typical applications of microfiltration process are in the
removal of bacteria from water samples and removal of submicron size suspended
dust and particulate matters from gas streams. Removal of chemical oxygen demand
from effluent waters is another important application of the MF process.

11.3.5 Dialysis

9
Other Separation Dialysis is a membrane process in which a microsolute permeates across a membrane
Methods as a result of concentration gradient from a given feed solution to another receiving
solution with a common solvent. The microsolutes permeate across the membrane
faster than the macrosolutes which are also present in the solution. The pore size of
the membranes are chosen in such a way to block the passage of macrosolutes. The
o
pore sizes of membranes used in dialysis typically ranges from around 20 A to
o
60 A or so. Commonly, the fluid phase from which the microsolutes are removed is
designated as feed phase whereas the fluid phase which receives the microsolutes is
designated as dialysate. The most common application of dialysis process is the
purification of blood to reduce the toxic end products of metabolism in a patient
whose kidneys have failed. It is the single largest application of dialysis process and is
known as hemodialysis or artificial kidney. This process is discussed in detail in
subsequent section of this unit.

11.3.6 Electrodialysis (ED)

In electrodialysis (ED) process, electrolytes are removed from one solution to the
other and it is used for desalination of saline waters. The cations and anions permeate
through cation selective and anion selective membranes, respectively as a result of
applied electrical energy. Even though reverse osmosis and electrodialysis are both
useful for desalination, there is a fundamental difference between the two. In RO, the
solvent permeates through the membranes and solutes, both electrolytes and
nonelectrlytes, are retained by the membranes. In ED, electrolytes permeate through
the membranes and, the solvent and nonelectrolytes generally do not permeate
through the membranes. The solution from which electrolytes are removed gets
depleted of salt and the solution which receives the solute gets enriched with salt. A
simple schematic of an electrodialysis process is given in Fig. 11.3.

Concentrated feed solution

AE, CE= Anion selective and cation selective membranes;
A,C = Anion and cation, respectively.
Fig. 11.3: A schematic representation of electrodialytic process
The process is used for desalination as well as production of table salt.The cation and
anion selective membranes used in this process are ion exchange membranes which
are nothing but ion exchangers in sheet form. Similar to cation exchange and anion
exchange resins, there are cation exchange and anion exchange membranes. This
process is discussed in detail in subsequent section of this unit.

10
11.3.7 Gas Separation Membrane Separation

The concept of separating gases using membranes is more than 100 years old, but the
widespread use of gas separation membranes has occurred only within the last decade.
Membranes separate gases only if some components pass through the membranes
more readily as compared to others. A typical membrane process for gas separation
operates with hydrostatic or partial pressure difference across the membrane as the
driving force. The feed gas mixture is fed to the membrane at an elevated pressure,
where it permeates across the membranes. The other side of the membranes is held at
a lower pressure. Separation is achieved because of differences in the selective
permeation rates of the feed gas components. Components that permeate more rapidly
across the membranes become enriched in the permeate stream while the slower
permeating components are concentrated in the residual or the retentate at high
pressure.

The degree to which gaseous components are separated is governed by the ability of
the membranes to discriminate between the two gases as well as the relative driving
force for each component. The solubility of the gases in the membrane matrix and the
diffusivity of the dissolved gas molecules are the main governing factors in the
selectivity. Many gas separating membranes are considered to be dense membranes.
The pore size of the membranes for use in gas separation membranes needs to be
much smaller than the mean free path of the permeating gas molecules. Details
regarding the mechanism involved in gas separation through membranes and the
relation between mean free path of the gas molecules and membrane pore size will be
dealt with in the next section. Important applications of gas separation using
membranes are in the production of high purity nitrogen from air, oxygen enrichment
from air and recovery of helium from natural gas.

11.3.8 Pervaporation
Pervaporation is a membrane separation process wherein a membrane separates liquid
feed and vapour permeate phases. Some of the components in the liquid feed phase
vapourises and permeates through the membranes and separation involves a phase
change. A schematic of pervaporation process is given in Fig. 11.4.

FeedFeed
mixture AAand B Permeate enriched with A or B
mixture and B
Permeate enriched wiht A or B
vacuum

pervaporation membrane
Pervaporation membrane

Fig. 11.4: A schematic representation of pervaporation process

It is a versatile method of separation of polar and nonpolar liquid mixtures and the
driving force for this kind of separation is the partial pressure difference of the
permeating components across the membranes. The gaseous permeate is usually held
at a low pressures and the liquid feed stream is at an elevated temperature to facilitate
evaporation of permeating components. Pervaporation is an attractive process for
separation of liquid mixtures which form azeotropes, i.e., where vapour and liquid
have the same composition in equilibrium and standard distillation cannot achieve the
separation. Important applications of pervaporation process are dehydration of alcohol

11
Other Separation and recovery and concentration of naturally occurring aroma compounds from dilute
Methods solutions.

11.3.9 Liquid Membrane Processes

The process as well as the mechanism involved in separation using liquid membranes
are briefly outlined before. As it is by now familiar, a membrane is simply a barrier
between two phases and if one component of a mixture moves through the membrane
faster than the other, separation is accomplished. A membrane is basically defined on
its separating performance and not necessarily it should be a solid. Liquids that are
immiscible with the source (feed) and receiving (product) phases can also be used as
membranes. Different solutes will have different solubilities and diffusion coefficients
in a liquid. The product of the diffusivity and the solubility is known as the
permeability coefficient which is proportional to the solute flux. The differences in the
permeability coefficients produce a separation between solutes at constant driving
force (concentration difference). Because the diffusion coefficients in liquids are
typically orders of magnitude higher than in solid matrices, a larger solute flux can be
obtained with liquid membranes. Further, the solute flux can be enhanced by adding a
nonvolatile complexing agent (carrier) to the liquid membrane. This carrier can
selectively and reversibly react with the solute. This reversible reaction provides a
means of enhancing the solute flux and improving the selectivity at the same time.

Liquid membranes are encountered in three basic configurations. In a bulk liquid

membrane (BLM), a relatively thick layer of immiscible liquid is used to separate the
source and the receiving phases. To provide thinner liquid membrane, the liquid can
be impregnated in the pores of a microporous membrane. This configuration is known
as an immobilised or supported liquid membrane (ILM or SLM). In the third
configuration which possesses the largest interfacial areas, the receiving phase is
emulsified in an immiscible liquid membrane. The emulsion liquid membrane (ELM)
is also known as liquid surfactant membrane. The emulsion liquid membrane is then
dispersed in the feed solution and the solute transport takes place from the feed phase
to the internal receiving phase.

Transport in supported liquid membranes

In the extraction of the metal ions , the carrier molecule in the membrane picks up
metal ions from the feed solution forming a complex. This complex diffuses to the
other side of the membrane where decomplexation occurs and the metal ions are
released into the receiving phase. Free carrier then diffuses back across the membrane
for use in another cycle. This coupled transport through SLM can take place by the
following processes.
* Co-transport

* Coupled transport
Coion transport in which both metal ions and its counterions are transported from the
feed solution through the SLM and into the receiving phase is shown in Fig. 11.5 (a).
If the carrier, C, is neutral, the driving force is the difference in distribution
coefficients ( Kd ) between the feed and receiving solutions . This is generally
achieved by maintaining a concentration gradient of the counterion X − between the
two solutions. This metal ion and counterion form a complex with the carrier , C, in
the membrane. This complex diffuses to the other side of the liquid membrane and the
metal ion and counterion are released into the receiver solution. The chemical reaction
for this coupled transport is
M n+ + nX + C (membrane) extraction CMXn (membrane)
... (11.4)

12
 CMXn (membrane) stripping C (membrane) + M n+ + nX Membrane Separation
... (11.5)
The liberated carrier molecule diffuses back to the feed solution -SLM interface, picks
up another metal ion and the counterion and the process continues until the final
equilibrium is attained.

Counterion transport (Fig. 11.5 b) in which an acidic carrier, HC , loses a proton and
forms a complex , MC, metal ion at the feed solution-SLM interface. This complex
diffuses to the SLM-strip solution interface where it liberates the metal cation into the
receiver phase and simultaneously picks up a proton from the strip solution. The
regenerated carrier, HC, diffuses back to the feed solution-SLM interface, picks up
another metal ion and the process continues. The acidic carrier molecule shuttles
between the feed and the strip solution-SLM interfaces.
n+ + n HC (membrane) extraction MCn (membrane) +
M n H+
... (11.6)

MCn (membrane) + n H+ stripping

n H+ + M n+
... (11.7)
The driving force in a counter transport SLM system is the pH difference between the
feed and the strip solution. For efficient transport, high feed and low strip solution, Kd
values are needed. The Kd difference between the feed and strip solution is maintained
by a pH gradient. For divalent metal ion and an acidic carrier, the reaction at the feed
solution-SLM interface is as follows:
M2+ + 2 HC → MC2 ( membrane ) + 2 H+ (aq) ... (11.8)
The equilibrium constant is given by the expression
[MC 2 ( membrane) ] [ H + (aq)]
Kd = … (11.9)
[ HC ( membrane) ] 2 [M 2+ ( aq ) ]

By inverting the concentration terms in Eq. 11.9 we get the equilibrium constant at the
receiving side of the membrane. The overall equilibrium constant is achieved when
there is no further metal ion transport from the feed to the receiving side and the
following relationship applies.
log [(M2+) receiving phase / (M2+) feed ] = 2 ∆ pH … (11.10)
where, ∆ pH is the pH difference between the feed and the strip solution. If for
example , the pH values for the feed and receiving solutions are 4 and 1, respectively ,
M2+ can be concentrated in the receiving solution to as high as 10 6 : 1 relative to its
concentration in the feed.

Feed phase Membrane phase Receiver phase

M ++ X C
CMX
C CMX M ++ X

(a)

13
Other Separation
Methods
M+

HC MC M+
HC MC
H+ H+
M M

(b)

Fig. 11.5: Transport Mechanism: (a) Co-transport and (b) Counter transport

SAQ 1
We have a mixture of protein, sucrose and calcium chloride in a solution in water and
we want to separate them from one another. Devise a combination of membrane
processes for accomplishing the same.

…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..

11.4 MECHANISMS OF SEPARATION THROUGH

MEMBRANES
The mechanism by which membrane exercises the property of selective permeation of
certain chemical substances is of utmost importance for a clear understanding of
membrane separation processes. The process of separation involves several
fundamental physical phenomena as the constituents in the feed pass over the
membrane surface, into it, through it and finally leave the membrane surface from the
other side. A generalised treatment of various mechanisms applicable in different
membrane processes are discussed in this section.

11.4.1 Sieving
The simplest type of membrane is one that functions merely as a sieve. If such a
membrane has to be effective, the solvent molecules must be much smaller than the
molecules or ions of the solutes and the pore size of the membranes must be
intermediate between the two. This condition is easily attainable in the case of
solutions where the solute is a macromolecule or a polymer where considerable size
difference exists between solute and the solvent molecules. In ultrafiltration and
microfiltration, sieving is one of the predominant mechanisms considered. However,
no sharp distinction exists between water molecules and small inorganic ions and
non-electrolytes and obviously sieving is not the mechanism by which a membrane
can retain small inorganic ions and small non-electrolytes and allow permeation of
water.

11.4.2 Solution-Diffusion
Solution-diffusion is often cited as the possible mechanism to explain selective
permeation of a chemical substance through membrane which is nonporous, from a
feed mixture where no appreciable size differences exist. For any chemical species to
permeate from one side of the membrane to the other side, it has to dissolve or absorb
in the membrane and subsequently diffuse through the membrane and get desorbed on

14
the other side. Consequently, certain components in the feed mixture get sorbed on the Membrane Separation
membrane in preference to other components due to chemical similarity or chemical
preference which could give the required selective permeation property to the
membrane.

Alternatively, when, in those cases where no significant changes exist in the sorption
behaviour of the components of the feed mixture, selective permeation still can arise
due to differences in their diffusion rates through the membranes. Chemical
substances with higher molecular mass diffuse slowly through the membranes as
compared to substances with lower molecular mass. The term permeation and
diffusion is alternatively used to describe the transport of chemical species across the
membranes. However, the distinction between them needs to be clearly understood.
The term diffusion specifically refers to random molecular motion of a species
yielding to a net transfer of that species from a region of higher concentration to a
region of lower concentration. The term permeation refers to a much more general
phenomenon of transfer of chemical species from one region to another under
different kinds of driving forces, namely, concentration gradient, pressure gradient,
electrical gradient or even temperature gradient.

If the membrane is viewed as a porous body in which solvent but not the solute is
adsorbed on the pore walls, this adsorbed solvent may so fill the pores such that there
is no room for the passage of solute molecules. Solvent molecules may pass through
by successive transfer from one adsorption site to the next. Since the association of
the adsorbed solvent molecules with the adsorbing site needs not be completely
broken down during the process, it requires relatively little energy, compared to that
required for a solute molecule to invade the mass of adsorbed solvent molecules. In
the case of desalination membranes, the adsorption of solvent molecules is brought
out by hydrogen bonding. Such membranes are known to allow permeation of those
solutes like ammonia, phenol, etc. which have hydrogen bonding tendencies similar to
that of water.

11.4.3 Preferential Sorption-Capillary Flow

Preferential sorption-capillary flow mechanism was the fundamental approach for the
practical development of reverse osmosis process for converting sea water into
potable water. If the surface of the membrane in contact with the solution is of such a
chemical nature that it has preferential sorption for water or preferential repulsion for
solutes then a multimolecular layer of preferentially sorbed pure water could exist at
the membrane surface. Continuous removal of this interfacial water can then be
effected by letting it flow under pressure through membrane capillaries. This concept
also defines a critical pore diameter required on the membrane surface for maximum
rate of withdrawal of pure water. This is obviously twice the thickness, t, of the
interfacial pure water layer. If the pore diameter is higher, then the rate of withdrawal
of water will be higher but the solute separation will be lower since not only the
adsorbed pure water but also bulk of the solution will also flow through the pores. If
the pore diameter is smaller, the solute separation could be maximum but the rate of
permeation will be reduced. The connecting pores in the interior bulk of the
membrane from the surface could be and should be bigger. These requirements are
essential from a practical point of view because, the total resistance to the permeating
water will be low.

11.4.4 Donnan Effect

Ion selective membranes show selective permeability towards ions of a particular
sign. Such membranes are ion exchangers in sheet form, a cation exchanger being
selectively permeable towards cation and an anion exchange showing the same

15
Other Separation behaviour towards anions. The chemical structure of ion exchange membranes
Methods consists of a network of carbon atoms and styrene nuclei with a suitable functional
group attached to the styrene nuclei. If the membrane is immersed in an aqueous
medium, it absorbs water and swells due to the affinity between the functional groups
and water. The functional groups dissociate to yield an electrically charged fixed
group chemically bound to the hydrocarbon matrix and a mobile ion carrying the
opposite charge. The latter are free to move under the influence of an applied
electrical field or to exchange with other ions of similar charge diffusing into the
membrane from the external solution.

Cation selective membranes contain negatively charged groups fixed to the

hydrocarbon matrix and a mobile cation. Anion selective membranes contain a
positively charged group fixed to the hydrocarbon matrix and a mobile anion. When
an ion selective membrane is in contact with an aqueous solution of an electrolyte,
those ions having the charge similar to that of the fixed group on the membrane
polymer matrix are designated as coions and those ions having charge similar to that
of the mobile ions are designated as counter ions. When the electrical equilibrium is
established between the ion selective membrane and the external electrolyte solution,
within the membrane phase, the charges of the fixed group is electrically balanced
with those of the counter ions from the external solutions as well as its own intrinsic
counter ions. The coions from the external solution are more or less excluded from the
polymer matrix. This type of exclusion is called the Donnan Exclusion and the
selectivity of ion exchange membranes arises due to Donnan effect.

11.4.5 Knudsen Flow

Knudsen flow or knudsen diffusion is one of the possible mechanisms cited to explain
the gas separation through membranes. When the mean free path of the gas molecules
is small compared to the pore size of the membranes, the permeation of gas molecules
is governed by viscous flow or hydrodynamic flow. The flow rate of the gas
molecules in viscous flow is directly proportional to the pressure gradient causing the
flow. Under such condition, the collision frequency between gas molecules exceeds
greatly as compared to the collision frequency of gas molecules with the pore wall of
the membranes. No specific separation of a particular gas component may be
expected, because of complete molecular chaos. However, when the mean free path of
the gas molecules is much larger than the membrane pore diameter, the collision
between gas molecules becomes much fewer than the collision between gas molecules
and the wall. The situation is known as rarefied gas and the flow under such
conditions is usually referred to as “free molecular diffusion” or “Knudsen Flow”. In
Knudsen flow the component gases flow through the membrane pores independently
of each other. Thus, a separation takes place due to the differences in the molecular
weight. This is the principle involved in the separation of U-235 isotope by means of
gaseous diffusion process.

11.4.6 Surface Flow

Permeation rates of gaseous molecules through the membranes may be enhanced in
some cases by surface diffusion mechanism. In surface diffusion, gas molecules
adsorb to the surface of the pores of the membranes and then diffuse along the pore
walls. High selectivity can be achieved in cases where preferential adsorption of one
of the components occurs. Surface flow is the result of solution diffusion mechanism
and is used to describe the preferential permeation rate of some gaseous components
through membranes from a given feed mixture and is similar to preferential sorption
capillary flow mechanism described previously for liquid feed systems. Separation of
condensible gases and vapours from noncondensible permanent gases through
membranes is often explained by surface flow. Such a separation is carried out at a

16
suitable temperature and pressure near or below the critical temperature of the gas. At Membrane Separation
high pressures, multilayer adsorption of gas molecules occurs at the pore walls
reducing the size of the pores. At a particular pressure, the entire pore volume is filled
with the permeating gas and the gas molecules are said to have condensed inside the
membrane pores, effectively blocking the passage of permanent gases. Such a
phenomenon is known as capillary condensation.

11.4.7 Facilitated Diffusional Transport

When a simple diffusion process is coupled with chemical reactions, the net
permeation rate may be greatly affected. Such a diffusional permeation is called
facilitated diffusional transport. Facilitated diffusion occurs in liquid membrane
systems. This mechanism requires a carrier substance (X) inside the membrane which
shuttles back and forth between the two sides of the membrane carrying the permeant
molecule (A). The schematic of facilitated diffusion which occurs in liquid
membranes is given in Fig. 11.6.

Fig. 11.6: A schematic representation of facilitated diffusion in liquid membranes

11.4.8 Active Transport

All the mechanisms discussed so far are for nonliving membranes, where permeation
of chemical substances takes place in the direction from high concentration to low
concentration. For living (biological) membranes, such as cell membranes the actual
mechanism of permeation are generally quite complicated. In some cases, a substance
may be transported through a cell membrane against its concentration gradient. This
does not mean that the second law of thermodynamics is violated. In addition to
diffusion process, there are other reactions occurring in the membrane that supplies
energy to the system. Thus, the cell is doing work to move the substance through the
cell membrane against a concentration gradient. Since the cell membrane is ‘actively’
transporting the matter, the term ‘active transport’ is used for such a process. A
schematic of active transport mechanism is given in Fig. 11.7, and is quite similar to
facilitated diffusion. The schematic explains the active transport of a chemical
substance A through cell membrane from low concentration to high concentration
with the help of enzymatic reactions at the two surfaces of the membranes.

Enzyme E1 near the surface of low concentration of A promotes the chemical reaction
between A and B to yield a compound AB within the cell membrane. Compound AB
will diffuse through the membrane to the other side where there is another enzyme E2
.This enzyme does just the opposite of what E1 does and expedites the decomposition
of AB into A and B.

17
Other Separation
Methods

High concentration of A Low concentration of A

Metabolic
pump

Fig. 11.7: A schematic representation of active transport in cell membranes

The component A diffuses out of the membrane to the high concentration side
because there is a local build up of A inside the membrane. The carrier molecule B is
too large to pass through the cell membrane and is contained within the membrane.
The two enzymatic reactions constitute a metabolic pump which generates power to
pump A against its concentration gradient. The accumulation of potassium ions in
cells is a well known example of active transport.

SAQ 2
Explain the importance of surface pore size for separation of salt and water by reverse
osmosis process in the context of preferential sorption-capillary flow mechanism.

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…………………………………………………………………………………………..
…………………………………………………………………………………………..

11.5 OSMOTIC PHENOMENA

When a salt solution is separated from pure solvent by a semipermeable membrane, a
membrane that permits the passage of solvent but not the solute, it is observed that
solvent tends to pass through the membrane into the solution and thereby, dilute it.
The phenomenon is called osmosis. Before proceeding, it is necessary to define a
quantity called the osmotic pressure (Π). For this purpose, consider Fig. 11.8.

Fig. 11.8: Osmotic pressure of salt solutions

A is a chamber open at one end and fitted with a movable piston B. The chamber is
divided by means of a semipermeable membrane C, into two sections, of which the
right one is filled with pure solvent, the other with some salt solution. Due to osmosis,
the solvent will tend to pass through the membrane into the solution and displace the
piston upward. The motion of the piston and the osmosis can be prevented, however,
by the application of pressure to the piston in order to keep it in the original position.
The mechanical pressure which must be applied to prevent osmosis of the solvent into
the solution through semipermeable membrane is called osmotic pressure of the

18
solution. This pressure for a given solution depends on a number of several solution Membrane Separation
properties. But this pressure does not depend on the nature of the membrane so long
as the membrane is truly semipermeable.

It is possible to derive, from purely thermodynamic considerations, an expression for

osmotic pressure in terms of measurable solution parameters. At any constant
temperature and pressure of one atmosphere, transfer of solvent into solution occurs
because the molar free energy of the pure solvent, µ0, (standard chemical potential of
the solvent) is greater than the partial molar free energy of the solvent in the solution
µi . To bring an equilibrium between the two and thus, stop osmosis, it is necessary to
increase the value of µi by applying higher external pressure on the solution. If this
increase in free energy is ∆µi , then the condition for osmotic equilibrium must be
µ i0 = µi + ∆ µ1 ... (11.11)

and hence
µi0 – µi = ∆ µ1 ... (11.12)

The chemical potential (µi) of component, i, in a solution is defined in terms of Gibbs

free energy (G) by the relation
dG = SdT + VdP +Σi µi dNi ... (11.13)
where, S is the entropy, T is the absolute temperature, V is the volume , P is the
pressure and Ni is the number of moles of component, i.

From Eq. 11.13,

µI = (∂G/ ∂Ni )T,P,N … (11.14)
and
V = (∂G/ ∂P)T, … (11.15)
where, N represents the entire set of N’s and Nj represents all N’s except Ni..

Differentiating Eq. 11.13 with respect to Ni

(∂ 2G/∂ Ni ∂P)T,N = (∂µi / ∂ P)T,N = (∂V/∂Ni )T,P,N = Vi … (11.16)

where, Vi is the partial molar volume of component, i.

The thermodynamic activity, ai of component, i is related to its chemical potential µi

by the relation
µi0 = µi * + RT ln ai … (11.17)
where, R is a gas constant.

In a binary aqueous salt solution system, let component, i represent water indicated by
subscript w and let µi = µ∗ (chemical potential of water at a specified pressure and
temperature). According to Eq. 11.17, the chemical potential of water µ w in the
solution at pressure P1 is less than that of pure water. ∗

µw = µw* + RT ln aw … (11.18)
where, aw is the thermodynamic activity of water in solution. The equilibrium can be
restored by increasing the pressure on the solution side to P2 such that the chemical
potential of water is raised to that of pure water, µw. The increase in chemical

19
Other Separation potential of water in the solution as the pressure is increased from P1 to P2 is obtained
Methods from Eq. 11.16.
P2 P2

∫
P1
(∂µw/∂P)T,N dP = ∫ Vw dP ... (11.19)
P1

Since this increase, added to µw must restore the chemical potential of water and
according to Eq. 11.19
P2
µw + ∫ P1
Vw d ∫P= µ*w … (11.20)

P2
∫P1
Vw dP = µ *w − µw … (11.21)

Vw ( P2 − P1 ) = − RT ln aw … (11.22)
when Vw is assumed constant.

The pressure difference (P2 –P1) is by definition the osmotic pressure of the solution,
usually represented by Π . Thus,
Vw Π = – RT ln aw … (11.23)

Π = – RT / V w lnaw … (11.24)
For calculating the activity of water in the solution, aw, , the vapour pressure data are
needed. Often aw is calculated from the relation
*
aw = Pw / Pw ... (11.25)
where, Pw is the vapour pressure of water in equilibrium with the solution at a
specified temperature, while Pw* is that of pure water at the same temperature.

If the solute is volatile, the partial vapour pressure of water must be used for Pw.
Substituting Eq. 11.25 in Eq. 11.24, we get
Π Vw = RT ln ( Pw / P*w ) …(11.26)
Eq. 11.19 can be reduced to a simpler form from the special case of dilute solution of
binary electrolyte obeying Raoult’s law. For such solution
o
P1 / P1 = N1 = (1–N2) … (11.27)
where, N1 and N2 denote the mole fraction of solvent and solute, respectively.

Eq. 11.26 can be written in terms of solute, mole fraction as follows:

Π Vw = − RT ln ( 1− N2) … (11.28)
If ln ( 1– N2 ) be expanded in series, then for dilute solutions all terms beyond the first
can be neglected, and ln (1–N2) becomes – N2 which is equal to n2/n1 where, n2 is the
number of moles of solute in n1 moles of solvent. Hence,
Π V w = RT n2/n1 ... (11.29)

and Π V w n1 = n2 RT ... (11.30)

20
But V w n1 is the total volume of solvent containing n2 moles of solute, which for Membrane Separation
dilute solutions is essentially the volume of the solution. Consequently,
ΠV = n2 RT … (11.31)
or alternately
Π = cRT … (11.32)
where, c is the molarity of the solution. Eq. 11.32 is well known as van’t Hoff’s
equation for ideal solutions. For electrolytes which ionise in solvent/ water, the
observed osmotic pressure is more than what is predicted from molar concentrations
data as the osmotic pressure is a colligative property of the solution which depends on
the number of species in solution. Accordingly, a correction term known as van’t Hoff
factor is introduced in Eq.11.25 as follows.

Π = icRT … (11.33)

The van’t Hoff factor is approximately equal to number of ions produced during
ionization per molecule of the electrolyte.

SAQ 3
Which will have a higher osmotic pressure, 5% calcium chloride solution or 5% urea
solution?

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…………………………………………………………………………………………..

11.6 REVERSE OSMOSIS PROCESS

Osmosis is a natural process wherein solvent/water passes through a semipermeable
membrane from the side with lower solute concentration to the higher solute
concentration side until equilibrium of solvent/water chemical potential is restored.
To reverse the flow of water, a pressure difference greater than the osmotic pressure
difference is applied. As a result separation of water from salt solutions becomes
possible. This phenomenon is termed reverse osmosis. It is also known as
hyperfiltration.

The process is generally evaluated in terms of parameters such as water flux, Jw,
solute separation, R and water recovery,Y. The definitions of these parameters are
given below.

The parameter water flux, Jw, refers to the amount of permeating solvent/water per
unit time per unit area of membrane.
Jw = Qp / A.t … (11.34)
where, Q is the quantity of permeating solvent/water per time, t, through membrane
area, A. The quantity Q may be expressed on weight basis, volume basis or molar
basis.

The separation of salt by membrane is commonly expressed as solute separation R,

21
Other Separation which is the fraction of salt in the feed that does not permeate through the membrane.
Methods
R = 1– Cp / Cf … (11.35)
where, Cp and Cf denote solute concentration in the membrane permeated stream (See
Fig. 11.1) and in the feed inlet stream, respectively.

Water recovery Y, is commonly used to define the percentage of feed water that is
converted into pure water in the permeate and is calculated as follows:
Y = (qp/qf ).100 … (11.36)
where, qp and qf denote the quantity of permeate stream and feed inlet per unit time,
respectively. .

11.6.1 Basic Equations

The process parameters as defined above depend on several factors such as the
physical structure and the chemical nature of the membranes, pressure, temperature,
nature and concentration of solute, flow rate of the feed salt solution along the
membrane surface etc. The nature of the dependence of these factors on the process
performance are analysed and a number of quantitative expressions are derived. A
detailed description of their mathematical aspect is beyond the scope of this unit. A
simplified expression for water flux and solute separation based on solution-diffusion
mechanism is given below.

In the solution-diffusion mechanism, the permeation of solvent as well as solute

through the membrane arises due to the dissolution of the permeating species in
accordance with an equilibrium distribution law and diffusion through membranes in
response to pressure and concentration gradient. An expression for water flux is given
by
Jw = Dw Cw V w (P –Π) / RT ∆x … (11.37)
where P and Π are respectively, the applied pressure and osmotic pressure of the feed
solution, ∆x is the thickness of the membrane, Dw and Cw , respectively refer to
diffusion coefficient and concentration of water in the membrane phase expressed as a
volume ratio and which is a dimensionless quantity.
__

The terms V w , R , T refer to partial molar volume of water, gas constant and
temperature, respectively. ,

The quantity Dw Cw V w / RT ∆x can be considered a membrane constant and denoted

by A whose magnitude depends on the physical structure as well as the chemical
nature of the membrane and the temperature of the feed. Accordingly, Eq. 11.37 can
be written as
J w = A(P – Π ) … (11.38)
Eq. 11.38 also indicates that the observed water flux across a membrane not only
depends on the value of membrane constant A, but also on the applied pressure and
osmotic pressure of the feed which is a function of solute molarity, its nature and
temperature. For a given applied pressure, if the solute concentration in the feed is
higher, its osmotic pressure will be higher and consequently, the observed water flux
will be lower. Alternatively, for a given feed solution with a definite feed
concentration, higher applied pressure will improve the observed water flux across the
membrane. It follows that for separating pure water from salt solution having higher
solute concentration, like sea water, a higher operating pressure is needed to maintain

22
the same driving force whereas lower operating pressures are sufficient for feed Membrane Separation
solutions of lower solute concentrations.

The solute also diffuses through the membrane simultaneously with water and the
solute flux, (JS) which is a measure of the quantity of solute, expressed in mass or
molar basis, diffusing through the membrane per unit time per unit area, is given by
JS = DS KS ∆CS / ∆x … (11.39)
where, ∆CS is the difference in solute concentration across the membrane, KS is the
distribution coefficient for the solute between feed solution near the membrane
surface and the membrane which is given again as a dimensionless parameter and DS
refers to the diffusion coefficient of solute in the membrane phase.

The quantity DSKS/∆x can be treated as solute permeation constant (B) whose
magnitude is characteristic of the membrane and the solute under consideration.
Accordingly, Eq. 11.39 may be written as
JS = B(∆CS) … (11.40)
Eq. 11.40 indicates that the solute flux through the membrane increases with increase
in solute concentration difference across the membrane which will manifest in lower
observed solute separation. The magnitude of solute flux depends on the value of
solute permeation constant (B).The desirable properties of semipermeable membranes
for use in reverse osmosis process is higher water flux and solute separation which is
possible for a membrane with a higher value of A and a lower value of B.
Consequently, the ratio of the two constants A/B is often used to describe the
semipermeable character of a membrane. Higher the value of A/B, the more selective
is the membrane for water against solute.

The solute concentration in the permeate is determined by the relative flow of solute
and water as follows.
Cp = JS /Jw … (11.41)
Combining Eqs. 11.41, 11.40, 11.38 and 11.35, an expression for solute retention R
can be obtained as given below:
R = 1 – Cp/Cf = A (P – Π )/ A (P – Π ) + B ... (11.42)
It should be noted that water flux and solute flux are inversely proportional to the
membrane thickness but solute retention R which is given in terms of the fluxes, is
independent of membrane thickness. The solute retention increases with net effective
pressure difference (P–Π) and the ratio A/B.

11.6.2 Concentration Polarization

Concentration polarization results from the build up of highly concentrated solute on
the membrane surface as compared to the bulk feed solution away from the membrane
surface. This occurs because water permeation at the membrane surface leaves the
more concentrated solute layer which must diffuse back into the bulk liquid.
Concentration polarization increases the osmotic pressure at the membrane surface,
which causes a reduction in water flux and an increase in salt diffusion across the
membrane. If the concentration of sparingly soluble salts in the boundary layer
adjacent to the membrane surface exceeds the solubility limits, precipitation or
scaling will occur on the membrane surface. At such high concentrations, colloidal
materials in the feed solution may also agglomerate and foul the membrane surface.

SAQ 4

23
Other Separation What are the desirable properties of semipermeable membranes for use in reverse
Methods osmosis process?

…………………………………………………………………………………………..
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…………………………………………………………………………………………..

11.7 DIALYSIS
Dialysis is a membrane separation process wherein solutes diffuse across a membrane
barrier by means of a concentration gradient. The rate of diffusion of a solute through
the membrane increases linearly with increase in concentration gradient and the
proportionality constant, namely the diffusion coefficient, D, is a characteristic
property of the solute for a given membrane. Diffusion coefficients decrease roughly
in proportion to the square root of molecular weight of solutes and consequently,
solutes with higher molecular weights diffuse slowly through the membranes.
To achieve selective permeation of solutes by dialysis process, a combination of
solute and membrane properties are chosen. The pore sizes of membranes are chosen
in such a manner to exclude large size macrosolutes. Also, the process is employed for
separating those solutes where an order of magnitude difference exists among
diffusion coefficient values.

Dialysis is a highly constrained process because the molecular diffusional rates are
slow and if the receiving solutions (dialysate) are not continuously removed, the
solute concentration on both sides of the membrane will tend to equalise, negating the
driving force for separation. The permeant species is not recoverable in pure form and
is necessarily more dilute in the dialysate than in the starting stream. For these
reasons, dialysis has been limited to specialised uses in pharmaceutical and medical
purposes where partial purification of the feed stream, rather than recovery of a
product is intended.

The most important parameter to characterize dialysis process is the diffusive solute
flux (JD) across the membrane which is given by
JD = K Dm ∆C/ ∆x … (11.43)
where Dm denotes solute diffusion coefficient in the membrane, ∆C is the
concentration gradient of solute across the membrane and K is the partition coefficient
defined as the ratio of solute concentrations between membrane and external solutions
on either side at equilibrium. Fig. 11.9 shows a typical concentration profile for
diffusive transport across a dialysis process.

Feed Dialysate

CFM

CF

CDM

24
 Fig. 11.9: Typical concentration profile in dialysis process Membrane Separation
In this example, the solute is less soluble in the membrane than in the external phases.

The partition coefficient K is given by

K = CFM / CF = CDM /CD … (11.44)
The product KDm /∆x is often termed membrane diffusive permeability (Pm) of the
solute. If two or more solutes are dialysing at the same time, the degree of separation
or enrichment is proportional to the ratio of their permeabilities. The closer the
diffusive permeability of a solute in the membrane is to that in free solution, the more
rapid will be the dialytic transport.
Pm = K DM/ ∆ x … (11.45)
and
JD = Pm ∆C … (11.46)
The above equations also indicate that the diffusive solute flux in dialysis process is
inversely proportional to the membrane thickness but the degree of separation among
different solutes (selectivity) is independent of membrane thickness. For this reason,
dialysis membranes are always made as thin as possible consistent with the
requirement of mechanical strength and reliability.

Another parameter, namely, intrinsic membrane resistance (RM) is also defined in

dialysis process.
RM = ∆x /KDM … (11.47)
RM value is characteristic of a particular membrane-solute system. The diffusive solute
flux is written in terms of resistance values as below.
JD = ∆C/RM … (11.48)
Solutions adjacent to membrane surfaces are rarely well mixed and the resistance to
diffusive transport resides not just in the membrane but also in the fluid regions,
termed stagnant boundary layers on both the dialysate and feed side. These stagnant
boundary layers offer additional resistance to diffusive solute flux and the overall
resistance (R0) is the sum of all the resistances in series.
R0 = RB +RM + RD … (11.49)
where, RB and RD refer to resistances offered by feed and dialysate side boundary
layers.

SAQ 5
What are the limitations of dialysis process?

…………………………………………………………………………………………..
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11.8 ELECTRODIALYSIS
Electrolysis is a membrane process wherein preferential transport of cations and
anions are achieved using cation and anion selective membranes as a result of an
electrical driving force. Using this process, the concentration of ionic species can be
increased or decreased so that practical concentration or depletion of an electrolyte
solutions is possible. With ion selective membranes of recent origin which are more
permeable to univalent cations or anions, electrodialysis process can be used to

25
Other Separation simultaneously separate and concentrate univalent ions from solutions containing
Methods mixtures of uni and multivalent electrolytes. The principle of this process has been
already explained (refer Fig. 11.3). Generally, the feed electrolyte solution where
cations and anions are removed, is termed dialysate and the receiving solutions where
the ions are added is termed as brine. During electrodialysis process, a number of
transport processes occur simultaneously which are illustrated in Fig. 11.10.

A C

conter ion transport C+H2O

co ion transport A+H2O
diffusion CA + H2O
+
osmosis H2 O

AE,CE= Anion selective, cation selective membranes, C,A,CA = cation, anion, electrolyte
Fig. 11.10: Various transport processes occurring in electrodialysis process

The counter ion (ion having opposite charge compared to that of the fixed group of
the membrane) transport constitutes the major electrical ion movement in the
process.Anion is the counter ion for anion selective membranes and cations are the
counter ions for cation selective membranes.The counter ion permeation through the
membranes carries with them a certain quantity of water by electro osmosis.

The coion (ion having similar charge as that of the fixed group of the membranes)
transport is comparatively small and is dependent upon the quality of the ion selective
membranes and brine concentration. Anion is the coion for cation selective
membranes and cation is the coion for anion selective membranes. Water is also
transported electroosmotically with the coions.

Diffusion of electrolytes occurs from the brine to the dialysate because in the
electrodialysis process the brine is usually more concentrated than the dialysate.
Water transport is also associated with electrolyte diffusion. Water transport due to
osmosis takes place from the low concentration dialysate compartment into the higher
concentration brine compartment.

The efficiency of electrodialysis process in the depletion of ionic substances from the
dialysate may be considerably reduced by the adverse effects, namely, coion
transport, free electrolyte diffusion, electroosmotic water transport associated with
counter ion movement and osmosis. The effects of these unwanted transfer processes
can, however, be reduced, by the selection of the membranes and by the operational
procedure.

Considering the above transport processes, ion selective membranes for use in
electrodialysis process should have a high selectivity for counter ions. The selectivity
of ion selective membranes may be expressed in terms of transport number of
counterions in the membrane phase ( t ) transport number is a measure of the fraction
of the total current carried by the counter ion through the membranes. This transport
number decreases as the salt concentration of the solution in contact with the
membrane increases. The term perselectivity (P) is also defined to characterize the
counter ion selectivity of membranes.
P = t – t / 1– t … (11.50)

26
where, t denotes the transport number of the ions in free solution. Membrane Separation

The ion selective membranes also need to have a high electrical conductance when in
equilibrium with the most dilute solution to be encountered in the process. The
membranes should permit only a negligible rate of free electrolyte diffusion under the
conditions of concentration difference expected in the process. As the concentration
difference across the membrane increases, free diffusion of electrolyte also increases.

The efficiency of electrodialytic process is given in terms of Coulomb efficiency (η).

Number of equivalents of electrolytes displaced from dialysate to the brine
η =
Number of Faradays of electricity passed in the process
… (11.51)
The unwanted transport processes, namely, coion transport, free electrolyte diffusion
and water transport contribute to the decrease in Coulomb Efficiency.

The rate of counter ion transfer flux ( J ) through membranes in electrodialysis

process is given by
J = t i /F … (11.52)
where, i is the current density (amperes per square centimetre area of membranes)
and F is the Faraday constant.

Similarly, the electrical ion fluxes (J) in the solution is given by

J= t i/F … (11.53)
Eqs. 11.45 and 11.46 indicate that the counter ion fluxes in solution as well as in the
membranes increase with increase in current density.

The flux of ions resulting from diffusion can be expressed in terms of Fick’s first
law.
[J]d = − D dc/ dx … (11.54)
At steady state, the combined electrical and diffusive flux through the membranes in
the boundary layers equals the electrical flux through the membranes and the
electrical flux through the membrane is the total flux.
J = t i/FZ = − D dc/dx + t i / FZ … (11.55)
Integration of Eq. 11.55 yields a simple relationship between boundary layer
thickness, δ, current density, i , interfacial concentration, Co, and the bulk
concentration , Cb.
Co = Cb + ( t − t) iδ / DFZ … (11.56)
Since t > t, i.e., the transport number of counter ions through membrane is more than
in solution, the ion flux in solution will be lower compared to their flux through the
membranes. The electrolytic movement of counter ions up to the membrane surface
will be insufficient to meet the faster rate of its migration through the membranes.
This difference will lead to depletion of counter ions on the dialysate side adjacent to
membrane and a build up of counter ions on the brine side adjacent to the membranes.
This is called concentration polarization and is schematically depicted in Fig.11.11.

27
Other Separation
Methods

Fig. 11.11: Concentration profile in electrodialysis

With increase in current density, the concentration polarization becomes more steep
and at sufficiently high current densities, the counter ion migration at layer adjacent to
the membrane in the dialysate approaches zero. Since there will not be any ions to
carry the current, any further current through the membranes will be carried by the
hydrogen and hydroxyl ions formed by the ionization of water at the interface. The
current at which this water splitting begins to occur is called the limiting current
density (ilim), because any further increase in current density would cause loss of
coulomb efficiency , increased electrical resistance and changes in the pH of the
solutions.

The limiting current density is described by setting Co = 0 in Eq. 11.56 in which case
ilim = C D Z/δ ( t – t ) … (11.57)
where C,D,Z and δ denote concentration of the ion in the bulk dialysate solution,
diffusivity in solution, electronic charge and thickness of the boundary layers,
respectively.

SAQ 6
Define Coulomb Efficiency in electrodialysis process and mention the factors
contributing to decrease in Coulomb efficiency.

…………………………………………………………………………………………..
…………………………………………………………………………………………..
…………………………………………………………………………………………..

11.9 APPLICATIONS
The membrane processes are used for separation of chemical substances and are of
immense interest for a wide range of commercial applications. The analytical
applications of membranes are grossly over shadowed by the industrial applications of
membranes. A complete and comprehensive discussion of all membrane based
applications would be very exhaustive and is beyond the scope of this unit. However,
a few major large scale applications of membranes will be discussed here.

11.9.1 Desalination and Water Treatment

Desalination of sea water (containing approximately 35000 to 40 000 milligrams of
dissolved salts per litre) and brackish waters (containing approximately 5000 to
10000 milligram of dissolved salts per litre) to produce potable water is one of the
widely known industrial applications of membrane processes. Reverse osmosis
processes to a large extent has been successfully used for the last two decades in
many parts of the world. In addition to desalination, reverse osmosis process is also

28
used for the treatment of municipal waste waters and effluents from the various Membrane Separation
chemical industries.

11.9.2 Protein Recovery

The most prominent use of ultrafiltration process is in the food industry, where it is
used ,for example to recover proteins from cheese whey, to concentrate milk before
cheese making and for fruit juice clarification.Other important applications of UF
process is in the removal of colour , odour and bacteria from the surface waters for
drinking water needs. The pore size of most of the UF membranes used for such
applications are such that they remove virtually all the microorganisms present in the
water and viruses to a large extent.

11.9.3 Production of Table Salt

Electrdialysis was first developed for the desalination of saline waters, in particular
brackish water. The production of potable water is currently the most important
industrial application of electrodialysis. One significant feature of electrodialysis is
that the salts can be concentrated to comparatively high values (in excess of 18 to
20 %) . The production of table salt from sea water by the use of electrodialysis to
concentrate sodium chloride up to 200 grams per litre prior to evaporation is a
technique developed extensively and used in Japan.

11.9.4 Hemodialysis
The most important application of dialysis process is in the artificial purification of
blood using a dialysis membrane and this process is called hemodialysis. In
hemodialysis, the impure blood from the patients flows across a dialysis membrane
and a physiological saline solution flows along the other side of membrane. This
process replaces kidney function in three principal areas, namely, removal of waste
metabolites, removal of excess body water and restoration of acid-base and electrolyte
balances. The waste metabolites include urea, uric acid, the end product of protein
metabolism and creatinine, the end product of muscle metabolism.

11.9.5 Ion Selective Membrane Electrode

The analytical applications of membranes are largely in the area of ion selective
membrane electrodes and particulate analysis. For most of the ion selective membrane
electrodes, the role of membranes is not to transport specific ions but to selectively
adsorb on either side giving rise to measurable electrical potential difference. A
particular membrane permits only a particular kind of ion to penetrate and adsorb. Ion
selective membrane electrodes have many applications in water analysis and
environmental monitoring. The principle of operation of membrane electrode is given
in Fig.11.12.

29
Other Separation Fig. 11.12: Basic principle of ion selective membrane electrode for metal ion
Methods determination
The electrical potential developed across the membrane, measured using ion selective
membrane electrode and reference electrode allows the determination of metal ion as
per Nerst equation given below.
E = 2.303 RT / n F log C/CS ... (11.58)
In principle, all factors associated with the use of the electrode, other than the ion
concentration to be measured, remain constant and the measurement of the cell
potential is directly proportional to the logarithm of ion concentration. A range of
different types of membranes are used in ion selective membrane electrodes, including
glass, solid state, heterogenous and liquid ion exchanger based. Table 11.1 gives a
selection of commercial ion selective membrane electrodes in which all the four types
are used.

Table 11.1: Typical Membranes and Commercial Ion Selective Membrane

Electrodes
Ion Membrane Concentration range Major interferences
electrode –1
(mol L )
+ –14
H Glass 10 to 1 None
+ –6
K Valinomycin 10 to 1 Ag+,H+ ,Li+
Na+ Glass 10 –6 to sat. Ag+, H+, Li+
F- LaF3 10 –6 to sat. OH¯ , H+
Cl - Ag2S /AgCl 10–5 to 1 Br –, I¯ , CN¯ , S2–
- –6
Br Ag2S /AgBr 10 to 1 I¯ , CN¯ , S2–
I- Ag2S / AgI 10–7 to 1 CN¯ , S2–
Table continued on next page
CN - Ag2S/AgI 10–6 to 10 –2 I¯ , S2–
S2– Ag2S 10–7 to sat. Hg 2+
Ag+ Ag2S 10–7 to 1 Hg2+
Cd2+ CdS/Ag2S 10–7 to 1 Ag+, Hg2+, Cu 2+
Pb2+ PbS/Ag2S 10–7 to 1 Ag +, Hg 2+, Cu 2+
Cu2+ CuS/Ag2S 10–8 to sat. Ag +, Hg 2 +, S2–
Ca2+ (RO)2PO2 -/(RO)3PO 10–5 to 10–1 Zn2+,Fe2+,Pb2+,Ca2+
Ca2+ + Mg 2+ (RO)2PO2-/ ROH 10–7 to 1 Cu2+,Zn2+,Fe2+,Ni2+,Pb2+
NO 3− R4N/ether 10–5 to 1 ClO4¯ , ClO3¯ , I¯ ,Br¯

Various types of glasses have been used as membrane electrodes in ion selective
membrane electrodes. When these electrodes were developed originally, they were
primarily used in measuring pH values. However, the scope of application has been
widened to include many univalent cations such as sodium, potassium, lithium,
ammonium, silver, rubidium, and caesium. Glass membranes are generally based on
Na2O–Al2O3–SiO2 mixtures. Membranes selective to hydrogen ions are rich in SiO2
whereas membranes selective to alkaline metal ions have a higher content of Al2O3 .

A variety of different solid state membranes are used for different ion detection. Many
of these use a combination of Ag2S + AgX (where X can be chloride, bromide, or
thiocyanide) in the form of a pressed disc and the electrode responds to X–. For the
determination of cations (Mn+), the membrane material is a mixture of Ag2S + Mn/2 S.

30
Heterogenous membranes use similar active components as solid state devices but Membrane Separation
instead the active material is deposited into the pores of an inert support like silicone
rubber or polyvinyl chloride plastic.

Ion selective electrodes based on liquid ion exchanger membranes immobilize an

active species, (an organic molecule dissolved in a solvent), into the pores of an inert
polymer. The typical active species are phosphate di esters for calcium ion detection,
metel complexes for anion detection and neutral macrocyclic crown ethers for alkali
metal detection.

11.9.6 Specific Gas Probes

Membranes are also used in specific gas probes for measuring dissolved gases and gas
phase partial pressures. The specific gas analysis is based on the electrochemical
oxidation or reduction of the gas at the appropriate electrode of an electrochemical
cell giving rise to a current whose magnitude depends on the concentration of the gas
consumed in the electrochemical reaction. The whole detection system is protected by
the membrane which is permeable to the particular gas component of interest. The
membrane can be polytetrafluoro ethylene, polyethylene, polypropylene, nylon or
cellophane. The membranes typically have pore sizes of several microns. Portable
devices for specific gas analysis are available for detection of gaseous oxygen,
hydrogen sulphide, carbon dioxide, sulphur dioxide, nitrogen dioxide and hydrogen
cyanide.

11.9.7 Detection and Analysis of Particulate Contamination

Microfiltration membranes offer a general way of removing particulate material from
fluid streams and are routinely used in a range of analytical procedures to determine
particulate contamination in gases and liquids. In general, these methods involve
passing a representative sample of liquid or gas through a suitable membrane. All
particulate matter which exceeds the membrane pore sizes are retained on the surface
where the contaminants may then be analysed.

11.9.8 Microbiological Analysis

Microporous membranes are important for the detection of microorganisms in foods,
beverages pharmaceutical products and potable water sources. The technique involves
the filtration of the samples through a microfiltration membranes to trap the
microorganism, then culturing the microorganism on the membrane and then counting
the grown colonies.

Another use of ultrafiltration is the preparation of plasma from the whole blood by
removing particulates.

11.10 SUMMARY
Now let us summarise the important aspects of membrane separations which we have
studied in this unit. Membrane processes use selective membranes for separation of
various chemical substances which can be either in suspended or dissolved states and
also in gaseous forms. Semipermeable membranes are physical barriers which allow
permeation of certain chemical constituents across them and effectively preventing
others from a feed mixture. Permeation of chemical substances requires a driving
force which can be either a pressure gradient, electrical potential gradient or
concentration gradient.

Gaseous permeation, reverse osmosis, ultrafiltration and microfiltration processes

utilise pressure gradient across the membrane. Dialysis and liquid membrane

31
Other Separation processes utilise concentration gradient. Electrodialysis process utilises electrical
Methods potential gradient as the driving force.

Mechanism of permeation of chemical substances through membranes basically

involve solution-diffusion and the permeating species dissolve in the membrane and
subsequently diffuse across. Preferential permeation across the membrane arises due
to the selective dissolution of the substances in the membrane and difference in their
diffusion rates through the membrane matrix. Chemical preference between the
membrane and the permeating substance, selective complexation within the
membrane and size compatibility between them may contribute to the separation
mechanism.

Osmotic phenomena occurs due to the difference in chemical potential between pure
solvent and solution and is the flow of solvent from pure solvent to solution through
semipermeable membranes. Reverse osmosis involves separation of solvent from
solution by application of pressure in excess of the osmotic pressure of the solution.

Dialysis process involves separation of low molecular weight solutes from high
molecular weight solutes by using concentration gradient across semipermeable
membranes of appropriate pore size and thickness. Electrodialysis process involves
separation of cations and anions using cation and anion selective membranes by
application of electrical potential.

Reverse osmosis and electrodialysis processes are mainly used for production of pure
water from naturally occurring saline waters and industrial effluents. They are widely
applied for producing drinking water and process water for industrial use as well as
for effluent treatment. Dialysis is mainly used for artificial purification of blood from
patients suffering from kidney failure. The protein metabolic products like urea, uric
acid and creatinine, etc. are separated from the blood stream in dialysis process.

11.11 TERMINAL QUESTIONS

1. Distinguish between osmosis and reverse osmosis, dialysis and electrodialysis
membrane processes.

2. What is facilitated diffusional transport mechanism and in which membrane

process it is mainly explained?

3. What are the parameters on which osmotic pressure of a salt solution depends?
Calculate the osmotic pressure of 1000 ppm calcium chlorideat 300 K?

4. Explain concentration polarization phenomena occurring in reverse osmosis

process?

5. What are important parameters to characterize dialysis process and discuss the
role of membrane thickness?

6. Discuss limiting current density and water splitting in electrodialysis process.

11.12 ANSWERS
Self Assessment Questions

32
1. Protein, sucrose and calcium chloride and water can be separated from each Membrane Separation
other by a combination of ultrafiltration, electrodialysis and reverse osmosis
processes. High molecular weight proteins can be separated from low molecular
weight sucrose and calcium chloride by ultrafiltration process. The permeate
from ultrafiltration process can be treated by electrodialysis to separate calcium
chloride which is ionic in nature. The dialysate from electrodialysis process can
be processed by reverse osmosis whereby sucrose can be concentrated and pure
water permeates through the membranes.

2. Separation of water and salt by reverse osmosis process is explained by

preferential sorption-capillary flow mechanism. This mechanism involves
formation of pure water layer at the membrane surface by preferential sorption
and its subsequent withdrawal through membrane pores by application of
pressure. To get maximum solute separation and permeation of water, the
diameter of the pore should not exceed twice the thickness of pure water layer.
If the pore size is more, the solute separation will be low and if the pore size is
less , rate of permeation will be less but solute separation will be more.

3. The osmotic pressure of a salt solution is given by

Π = iC RT
5% CaCl2 solution means 5 grams of calcium chloride in 100 grams of
solution

∴ Molarity of CaCl2 solution = 5 × 1000 / 100 × 110.98

= 0.451 moles/ litre

van’t Hoff factor, i = 3, R = 0.082 litre atmosphere per degree per mole,
T = 300 K
∴Osmotic pressure of CaCl2 solution = 3 × 0.451 ×0.082 × 300
= 33.28. atm
Similarly, molarity of 5% urea solution = 5 × 1000 / 100 × 60.032
= 0.833 moles / litre∗
i for urea = 1 since it does not ionise

∴osmotic pressure of 5% urea solution = 1 × 0.833 × 0.082 ×300

= 20.49 atm
∴5% CaCl2 solution has higher osmotic pressure
∗In the above calculation the density of solutions is taken as unity for
simplification.

4. The desirable properties of semipermeable membranes in reverse osmosis

process is maximum solvent permeation and minimum solute permeation. For a
given solute solvent system, the solvent permeation rate through different
membranes is decided by the pure water permeation constant (A) under identical
operating conditions.

Similarly, the solute diffusion rate for different membranes is decided by the
solute permeation constant (B) under identical solute concentration and
operating conditions. The higher value of the ratio of the constants A/B
indicates the most desirable property for a semipermeable membrane.

5. Dialysis is a diffusive process and since the molecular diffusional rates of

solutes are slow, the entire process tends to be slow and time consuming. If the
receiving solutions (dialysate) are not periodically removed, the solute

33
Other Separation concentration on both the sides of the membranes tends to equilalise, negating
Methods the driving force for separation. The permeant species is not recoverable in the
pure form and is necessarily more dilute in the dialysate than in the starting
stream.

6. Coulomb efficiency indicates the efficiency of the electrodialysis process and is

defined as the ratio of number of equivalents of electrolytes displaced from
dialysate to the brine, to the number of faradays of electricity passed. It is
generally expressed in percentage. The unwanted transport processes, namely,
coion transport, free electrolyte diffusion and water transport accompanying ion
transport across the membranes contribute to the decrease in coulomb
efficiency.

Terminal Questions
1. Osmosis is a process in which pure solvent permeates through a semipermeable
membrane when a pure solvent is separated from a solution by a semipermeable
membrane. This occurs due to the difference in chemical potential gradient
which is higher for pure solvent than in solution. Osmosis will occur when two
solutions with different solute concentrations are separated by a semipermeable
membrane and the flow of solvent will be from lower solute concentration side
to higher solute concentration side. Reverse osmosis process is an extension of
osmosis process wherein solvent is allowed to flow from the solution by the
application of pressure in excess of the osmotic pressure of the solution.

Dialysis process is driven by concentration gradient and involves molecular

diffusion of solutes, ionic as well as nonionic. Electrodialysis process is driven
by electrical potential gradient and involves mainly electrical migration of ions
of either charge.

2. When a simple diffusion process occurring across a semipermeable membrane

is coupled with chemical reactions within the membrane, the net diffusional rate
of permeating species through the membrane may be greatly enhanced. Such a
diffusional permeation is called facilitated diffusional transport. Facilitated
diffusion occurs in liquid membrane systems. This mechanism requires a carrier
substance inside the membrane which shuttles back and forth between the two
sides of the membrane carrying the permeating substance by combining with it.
Forward reaction of chemical combination between the carrier and the
permeating substance takes place on one side of the membrane and the
backward reaction of dissociation into carrier and the permeant occurs on the
other side.

3. The osmotic pressure of a salt solution depends on its molar concentration (C),
temperature (T), and the nature of the substance whether ionic or nonionic. If it
is a strong electrolyte, the number of ions it dissociates into upon ionization per
molecule (i) is also used in computing the osmotic pressure of the solution. If it
is a weak electrolyte, the degree of dissociation is used to compute the osmotic
pressure.

The molar concentration of 1000 ppm calcium chloride (C) = 9.01 × 10–3
moles / litre

T = 300 K, i = 3, R = 0.082 litre atm/degree/mole.

∴ Osmotic pressure of 1000 ppm calcium chloride =
3 × 9.01 × 10–3 × 0.082 × 300 = 0.665 atm.

34
 Membrane Separation
4. Concentration polarization is a phenomenon occurring in reverse osmosis
process due to the build up of a layer of highly concentrated solution near the
membrane surface as compared to the bulk feed solution. This occurs because
water permeation through the membrane leaves the more concentrated solution
layer near the membrane surface which must diffuse back into the bulk liquid
layer. Concentration polarization increases the osmotic pressure of the salt
solution near the membrane which causes a reduction in water flux across the
membrane and an increase in the solute diffusion through the membrane.

5. The important parameters characterizing dialysis process are the diffusive

solute flux (JD) across the membrane, which is directly related to concentration
difference across the membrane (∆C) , the solute diffusion coefficient in the
membrane phase (Dm) the partition coefficient for the solute with respect to the
membrane and the external solution (K) and inversely proportional to the
membrane thickness (∆x). The term (KDm /∆x) is collectively known as
membrane diffusive permeability (Pm). The higher the value of Pm , the faster
will be its rate of permeation through the membrane. Since Pm is inversely
related the membrane thickness, the thickness of the membrane needs to be less
to achieve faster rate of diffusion. For this reason, dialysis membranes are made
as thin as possible consistent with the requirement of mechanical strength.

6. The electrical migration of cations and anions in electrodialysis process is much

faster through the ion selective membranes than in solutions. Consequently,
cations and anions are not supplied from the dialysate solution side to the
respective side at a sufficiently faster rate by which they are carried through the
membrane. Similarly, once ions reach the other side of membranes they are not
quickly carried into the bulk of the solution on the brine side. This results in
depletion of ionic concentration on one side and build up of ionic concentration
on the other side of membranes. This is called concentration polarization and
this will become more severe with increase in operating current density. At
sufficiently high current density, the concentration of ions near the ion selective
membrane on the dialysate side drops to zero and the current is carried by the
hydrogen and the hydroxyl ions of water. This causes further ionization of water
and in effect, the electrical driving force applied, to carry the ions, is utilised to
split water instead. This phenomenon is detrimental to the process efficiency
and is known as water splitting. This causes Joule heating also. The current
density at which this phenomenon begins to occur is called the limiting current
density. Electrodialysis process is to be operated below the limiting current
density.

Further Reading

1. Handbook of Industrial Membranes, By Keith Scott, Elsevier Advanced

Technology, Oxford, 1995.

2. Membrane Handbook, By W.S.Winston Ho and Kamlesh K. Sirkar, Van

Nostrand Reinhold, New York, 1992.

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