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Membrane Separation
Structure
11.1
Introduction
Objectives
11.2
11.3
11.4
11.5
11.6
Osmotic Phenomena
Reverse Osmosis Process
Basic Equations
Concentration Polarization
11.7
11.8
11.9
Dialysis
Electrodialysis
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
11.11
11.12
11.1
Summary
Terminal Questions
Answers
INTRODUCTION
In Unit 1 of this course, two types of classifications for different separation methods
were proposedone 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 (subSec. 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
Methods
suspended particles from a turbid solution, separation of dissolved solutes from saline
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
define the terms like product flux, solute retention percentage, percent recovery,
membrane fouling and concentration polarization,
11.2
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.
Membrane
Membrane Separation
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
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 ) /
(11.1)
Other Separation
Methods
For two species A and B permeating across a membrane, the selectivity coefficient for
species A with respect to B ( 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 =
... (11.3)
11.3
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.
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.
Pressure in excess of
osmotic pressure
Membrane Separation
Semipermeable membrane
Solution
Pure water
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.
11.3.5 Dialysis
9
Other Separation
Methods
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.
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
Membrane Separation
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
mixture
and B
pervaporation membrane
Pervaporation membrane
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
Methods
and recovery and concentration of naturally occurring aroma compounds from dilute
solutions.
12
extraction
CMXn (membrane)
... (11.4)
CMXn (membrane)
stripping
C (membrane) + M n+ + nX
... (11.5)
Membrane Separation
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) +
stripping
MCn (membrane) + n H+
n H+
n H+ + M n+
... (11.6)
... (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)
(11.9)
( 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
/ (M2+) feed ] = 2 pH
phase
(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
M ++ X
Membrane phase
Receiver phase
C
CMX
C
CMX
M ++ X
(a)
13
Other Separation
Methods
M+
HC
H+
M
M+
MC
HC
MC
H+
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
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 in preference to other components due to chemical similarity or chemical
preference which could give the required selective permeation property to the
membrane.
Membrane Separation
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.
Other Separation
Methods
16
suitable temperature and pressure near or below the critical temperature of the gas. At
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.
Membrane Separation
17
Other Separation
Methods
Low concentration of A
High concentration of A
Metabolic
pump
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.
..
..
..
11.5
OSMOTIC PHENOMENA
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
properties. But this pressure does not depend on the nature of the membrane so long
as the membrane is truly semipermeable.
Membrane Separation
i0 = i + 1
... (11.11)
and hence
i0 i = 1
... (11.12)
... (11.13)
I = (G/ Ni )T,P,N
(11.14)
V = (G/ P)T,
(11.15)
and
where, N represents the entire set of Ns and Nj represents all Ns except Ni..
Differentiating Eq. 11.13 with respect to Ni
( 2G/ Ni P)T,N = (i / P)T,N = (V/Ni )T,P,N = Vi
(11.16)
i0
i *
RT ln ai
(11.17)
w*
+ RT ln aw
(11.18)
19
Other Separation
Methods
P2
(w/P)T,N dP =
P1
Vw dP
... (11.19)
P1
Since this increase, added to w must restore the chemical potential of water and
according to Eq. 11.19
w +
P2
P2
P1
Vw d
P=
*w
(11.20)
Vw dP = *w w
(11.21)
Vw ( P2 P1 ) = RT ln aw
(11.22)
P1
(11.23)
(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)
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 Raoults law. For such solution
o
P1 / P1 = N1 = (1N2)
(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:
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 (1N2) becomes N2 which is equal to n2/n1 where, n2 is the
number of moles of solute in n1 moles of solvent. Hence,
20
V w = RT n2/n1
... (11.29)
and
... (11.30)
V w n1 = n2 RT
But V w n1 is the total volume of solvent containing n2 moles of solute, which for
dilute solutions is essentially the volume of the solution. Consequently,
V = n2 RT
Membrane Separation
(11.31)
or alternately
= cRT
(11.32)
where, c is the molarity of the solution. Eq. 11.32 is well known as vant Hoffs
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 vant Hoff
factor is introduced in Eq.11.25 as follows.
= icRT
(11.33)
The vant 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?
..
..
..
..
11.6
(11.34)
Other Separation
Methods
which is the fraction of salt in the feed that does not permeate through the membrane.
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. .
(11.37)
where P and 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 )
(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
solutions of lower solute concentrations.
Membrane Separation
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)
(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 )/ A (P ) + 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) and the ratio A/B.
SAQ 4
23
Other Separation
Methods
What are the desirable properties of semipermeable membranes for use in reverse
osmosis process?
..
..
..
11.7
DIALYSIS
JD = K Dm C/ x
Dialysate
CFM
CF
CDM
24
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)
JD = Pm C
(11.46)
and
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)
(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?
..
..
11.8
ELECTRODIALYSIS
Other Separation
Methods
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
26
t t / 1 t
(11.50)
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 ().
(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 Ficks 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)
(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
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/ ( t t )
(11.57)
where C,D,Z and 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.
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used for the treatment of municipal waste waters and effluents from the various
chemical industries.
Membrane Separation
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.
29
Other Separation
Methods
Fig. 11.12: Basic principle of ion selective membrane electrode for metal ion
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
electrode
Membrane
Concentration range
Major interferences
(mol L )
10
14
to 1
None
Valinomycin
10
to 1
Ag+,H+ ,Li+
Na+
Glass
10 6 to sat.
F-
LaF3
10 6 to sat.
OH , H+
Ag2S /AgCl
105 to 1
Br , I , CN , S2
Glass
Cl Br
Ag2S /AgBr
10 to 1
I-
Ag2S / AgI
107 to 1
CN S2
Ag+
Cd2+
Pb2+
Cu2+
Ca2+
Ca2+ + Mg 2+
NO 3
Ag2S/AgI
Ag2S
Ag2S
CdS/Ag2S
PbS/Ag2S
CuS/Ag2S
(RO)2PO2 -/(RO)3PO
(RO)2PO2-/ ROH
R4N/ether
106 to 10 2
107 to sat.
107 to 1
107 to 1
107 to 1
108 to sat.
105 to 101
107 to 1
105 to 1
I , CN , S2
CN , S2
Table continued on next page
I , S2
Hg 2+
Hg2+
Ag+, Hg2+, Cu 2+
Ag +, Hg 2+, Cu 2+
Ag +, Hg 2 +, S2
Zn2+,Fe2+,Pb2+,Ca2+
Cu2+,Zn2+,Fe2+,Ni2+,Pb2+
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
Na2OAl2O3SiO2 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
instead the active material is deposited into the pores of an inert support like silicone
rubber or polyvinyl chloride plastic.
Membrane Separation
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
Methods
2.
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.
5.
What are important parameters to characterize dialysis process and discuss the
role of membrane thickness?
6.
11.12 ANSWERS
Self Assessment Questions
32
1.
Protein, sucrose and calcium chloride and water can be separated from each
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.
3.
Membrane Separation
= 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
vant 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.
5.
Other Separation
Methods
Terminal Questions
1.
2.
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) =
moles / litre
T = 300 K, i = 3, R = 0.082 litre atm/degree/mole.
Osmotic pressure of 1000 ppm calcium chloride =
3 9.01 103 0.082 300 = 0.665 atm.
34
9.01 103
Membrane Separation
4.
5.
6.
Further Reading
1.
2.
35