Electro-Membrane Processes PDF

ELECTRO-MEMBRANE PROCESSES
Ajay K. Singh and Vinod K. Shahi

Central Salt and Marine Chemicals Research Institute, Council of Scientific & Industrial Research
(CSIR), Bhavnagar, Gujarat, India
1 INTRODUCTION
Currently, electromembrane separation processes such as electrolysis, electrodialysis

(ED), reverse electrodialysis (RED), diffusion dialysis (DD), etc. are used on large indus-
trial scales in the production of potable and industrial process water as well as in the
treatment of industrial effluents (1). Presently, desalination of brackish water (2), blue
energy production (3), fuel cells (4), diary applications (5), HI concentration from HIx
mixed (HI—H2 O—I2 ) solution (6), chromic acid recovery (7), organic acid separation and
recovery (8, 9), ionic liquids synthesis (10), tetrabutylammonium hydroxide (TBAOH)
production (11), low water-soluble organic acids from their salts (12), DD for acids and
base recovery from waste acids (13), salts separation from mixed salts and organic solu-
tions, separation of cation and anions from wastewater, demineralization of sugar and
amino acids (AAs) (14), etc. are the application of electromembrane processes (EMPs).
Ion-exchange membranes (IEM) are key components in electrochemical processes for
separation, in situ ion substitution, and water splitting, and resemble ion-exchange resins
(IERs) in the sheet form. There are two types of IEMs: (i) cation-exchange membranes
(CEMs), in which negatively charged groups are fixed into polymer membrane matrix,
and (ii) anion-exchange membranes (AEMs) in which positively charged groups are
fixed into polymer membrane matrix. Fixed negative charges present in the CEM come
to equilibrium with movable cations, as shown in Figure 1. CEMs mainly allow cation
transfer through the membrane matrix due to the exclusion of co-ions, while AEMs
allow anion transfer through the polymer membrane matrix (Fig. 1). Electrochemical and
physicochemical properties of IEMs are dependent on their fixed charge concentration
and their hydrophobic/hydrophilic nature. The extent of co-ions excluded from IEMs
does not depend only on membrane properties but also on concentration of the feed
solution. High permselectivity, low membrane resistance, high mechanical, chemical, and
thermal stabilities are desirable properties of membranes that are used in membrane-based
electrochemical processes for separation, ion substitution, and water splitting.
Encyclopedia of Membrane Science and Technology. Edited by Eric M.V. Hoek and Volodymyr V. Tarabara.
Copyright © 2013 John Wiley & Sons, Inc.
1
2 ELECTRO-MEMBRANE PROCESSES
CEM AEM
+
+ – – – + – +
–
+
– – + + –
+ – – +
+
– + + –
+ – – + – + –
–
– – +
– + +
+ + – –
– + + –
+ + –
+ – + –
– – +
– – –
+ +
+ +
+ – + – +
(a) (b)
+ – Fixed ionic groups

+ – Free ions
FIGURE 1 Schematic presentation of (a) CEM and (b) AEM.
Desired membranes properties can be controlled by functionalization of base

material and fixed charge concentration. Fixed charge concentration determines
permselectivity and also influences the mechanical and swelling properties. The
following moieties are present in the membrane matrix as fixed charges in CEMs:
–SO3− , –COO− , PO3 2− , –PHO2 − , –AsO3 2− , and –SeO3− , while in the AEM matrix, they
are –N+ H2 R, –N+ HR2 , –N+ R3 , –+ PR3 , and –S+ R2 . Among the all cation-exchange
groups, –SO3 H is completely dissociated over the entire pH range, while the −COOH
group is undissociated at pH of less than 3.0. The quaternary ammonium group is
completely dissociated over entire pH, range while secondary the ammonium group is
weakly dissociated. Thus, IEMs should be stable in acidic and alkaline media.
The most desired properties of IEM are high permselectivity, low electrical resistance,
good mechanical and form stability, high chemical and thermal stabilities, and low pro-
duction cost. The commercial membranes available today meet most of the required
properties (Tables 1 and 2). But there are large differences in the properties of IEM. The
fluorocarbon polymer-based Nafion-type® CEM, for example, has satisfactory chemical
and thermal stabilities, but its production cost is presently extremely high. Most heteroge-
neous membrane structures have relatively low production costs, but their permselectivity
is generally low and their electrical resistance is high.
2 RECENT DEVELOPMENTS IN ION-EXCHANGE MEMBRANES (IEMs)
Because of the high production cost of the fluorocarbon-based polymer Nafion, a new
solid polymer electrolyte for the transport of ions with low cost and the desired properties
has been developed recently. Many researchers have developed different types of IEM
using different methods.
2.1 Heterogeneous Ion-Exchange Membranes

Heterogeneous IEMs have embedded fine IER particles in an inert binder such as
polyethylene (PE), phenolic resins, and polyvinylchloride (PVC). Heterogeneous IEMs
TABLE 1 Properties of Commercial Ion-Exchange Membranes (CEMs and AEMs)
Company Membrane Type IEC, mEq/g Thickness, mm Area Remarks
Resistance,
cm2
FuMA-Tech GmbH, Germany FKS CEM 0.9 0.09–0.110 2.0–4.0 Standard CEM
FKB CEM 0.8 0.10–0.115 5.0–10 For EDBPM
FAS AEM 1.1 0.10–0.120 2.0–4.0 Standard AEM
Tokuyama Co., Japan Neosepta CMS CEM 2.0–2.5 0.14–0.17 1.5–3.5 Monovalent
selective
Neosepta AM AEM 1.8–2.2 0.12–0.16 1.3–2.0 Low Rm
Neosepta ACS AEM 1.4–2.0 0.12–0.20 3.0–6.0 Monovalent
selective
Neosepta AFN AEM 2.0–3.5 0.15–0.18 0.20–1.0 Diffusion dialysis
Ionics Inc., USA 61CZL386 CEM 2.60 0.63 9.0 Monovalent
selective
CR67-HMR CEM 2.1–2.45 0.53–0.65 7.0–11 ED
AR103QDP AEM 1.95–2.20 0.56–0.69 14.5 ED
Solvay S.A., Belgium Morgane CDS CEM 1.7–2.2 0.13–0.17 0.70–2.1 Standard CEM
Morgane CRA CEM 1.4–1.8 0.13–0.17 1.8–3.0 Acid
preconcentration
Morgane ADP AEM 1.3–1.7 0.13–0.17 1.8–2.9 Demineralization
DuPont Co., USA Nafion 117 CEM 0.90 0.20 1.5 EMP (ED and
EED)
Nafion 901 CEM 1.1 0.40 3.8 EMP
CSMCRI, Bhavnagar, India IPC CEM 1.4 0.14–0.16 1.5–2.0 ED and EDI
HGC CEM 0.67–0.77 0.22 –0.25 2.0–4.0 ED
IPA AEM 0.80–0.90 0.16–0.18 4.0–6.0 ED
HGA AEM 0.40–0.50 0.22–0.25 5.0–7.0 ED
3
4
TABLE 2 Properties of Commercial Bipolar Membranes
Company Membrane Voltage Thickness, Efficiency, Remarks
Drop, V mm %
FuMA-Tech GmbH, FuMA-Tech <1.8a 0.450 >92b Ultrapure water: Anion-selective layer, polysulfone with bicyclic
Germany FT-FTBPM amines; cation-selective layer, sulfonated, cross-linked
polyether ether ketone; junction, insoluble polyelectrolyte
complex containing tertiary ammonium groups
FuMA-Tech <1.2a 0.180 >99b Amino acid separation, IEX-REC
FT-FBI
Aqualytics <1.1a 0.250 >98b For inorganic salts
FT-AQL-S1
Aqualytics <1.1a 0.200 >99b For organic salts
FT-AQL-P6
Tokuyama Co., Japan Neosepta 0.95 1.20–2.2c <98c Standard BPM: Anion-selective layer, aminated polysulfone;
cation-selective layer, Neosepta CM-1; junction, Fe(III)
hydroxide
WSI Technologies WSI — — 97b Anion-selective layer, Pall/Raipore R1030, ca. 70 mm;
Inc., USA cation-selective layer, Pall/Raipore R1010, ca. 40 mm,
nonreinforced perfluorinated; junction, chromium(III)
hydroxide
Graver water Co., Aqualytics BP6 — — — Polystyrene matrix to which quaternary ammonium and sulfonic
USA groups are attached
Kuban State MB — — — Anion-selective layer containing secondary, tertiary, and
University, Russia quaternary amines; cation-selective layer, sulfonic acid groups
in polyethylene binder, ca. 100 mm
Tianwei Membrane TWBPM 1.5–2.1 0.20–0.30 for EDBM stacks
Technology Co.
Ltd., China
a
Voltage drop at kA/m2 in 0.50 N Na2 SO4 at 30 ◦ C.
b
Efficiency at 1 kA/m2 in 1.0 N NaOH and HCl.
c
c Water-splitting efficiency of BP-1 for 1.0 N NaCl at 10 A/dm2 current density.
ELECTRO-MEMBRANE PROCESSES 5
are characterized by their conducting and nonconducting phases. Two methods are being
used to prepare these membranes: (i) mixing the IER powder with a binder and extruding
the membrane in sheet form and (ii) dispersion of IER particles into the polymer solution
and casting the solution into thin films. Furthermore, the solvent is allowed to evaporate
at ambient temperature. Sulfonated polystyrene-based cation-exchange resin (CER) is
dispersed in a vulcanizing silicon rubber solution, with low density polyethylene (LDPE)
as binder (15). Shahi et al. (16) reported polycarbonate (PC) and polysulfone (PS) based
heterogeneous CEMs and carried out chronopotentiometric studies to assess their suit-
ability for use in electromembrane separation processes. Acrylonitrile–butadiene–styrene
(ABS)/high impact polystyrene (HIPS) blended heterogeneous CEMs were also prepared
by dispersing CER powder into an ABS solution in tetrahydrofuran (THF) (17).
2.2 Homogeneous Ion-Exchange Membranes

Various methods are used to prepare homogeneous IEMs such as (i) monomer are poly-
merized to form copolymers, one of which should have cationic/anionic groups; (ii)
chemical grafting is carried out to introduce cationic/anionic groups in to the mem-
brane matrix; and (iii) synthesis of the functionalized polymer is done by chemical
routes. Different thermoplastics, such as PS, poly(ether sulfone) (PES), poly(ether ether
ketone) (PEEK), polyimide, etc., have been used to anchor the functional groups and
further in membrane fabrication. Commercial CEM and AEM are prepared from styrene
(St) and divinylbenzene (DVB) copolymer, and acidic (–SO3 H) groups are introduced
by sulfonation while basic (–+ N(CH3 )3 Cl− ) groups are introduced into the membrane
matrix are anchored in two steps: (i) chloromethylation of (St–DVB) copolymer and
(ii) quaternization of –CH2 Cl groups with tertiary amine (1). Friedal–Craft reactions
such as nitration, formylation, and sulfonation have been used to graft various func-
tional groups onto the St–DVB copolymer polymeric matrix (1). Interpolymer CEMs
have been prepared by St–DVB copolymer grafting onto PE film, and chlorosulfonic
acid (ClSO3 H) in ethylene dichloride and sulfonation was used as sulfonation reagent
to graft –SO3 H groups. Resultant membranes were characterized in terms of perms-
electivity and conductivity to assess their suitability in electro-driven membrane pro-
cesses (18). Various reports are available in which CEMs were prepared by radiation
grafting of St and DVB monomer onto the inert polymers poly(tetrafluoroethylene-
co-perfluorovinylether) (PFA), poly-(tetrafluoroethylene-co-hexafluoropropylene) (FEP),
PVC, LDPE, porous polypropylene (PP), and polytetrafluoroethylene (PTFE). CEMs
were prepared from St–DVB copolymer and PVC as binder. Further, various functional
groups (–PO3 H2 , –COOH, and –SO3 H) were anchored by phosphorylation, carboxy-
lation, and sulfonation (19). PP-based CEMs were prepared by radiation grafting of
glycidyl methacrylate (GMA) onto PP membranes and acidic groups were anchored
by sulfuric acid as the sulfonation reagent (20). A series of AEMs were also prepared
by radiation grafting of vinylbenzyl chloride (VBC) onto the partially or completely
fluorinated polymer films of poly(ethylene-co-tetrafluoroethylene) (ETFE), FEP, and
poly(vinylidene fluoride) (PVDF) for electrochemical processes (21). Kumar et al. pre-
pared St-AN monomer-based AEMs by free-radical polymerization in presence of a dual
initiator and further coating of the copolymer solution onto a ceramic clay support. Basic
groups in the membranes matrix were introduced in two steps, namely, (i) gas-phase nitra-
tion and (ii) amination by reduction and quaternization (22). Weakly acidic CEMs were
prepared from St–DVB copolymer, and weak acidic groups (–COOH) were anchored
by acetylation using chloroacetic acid. The developed membranes were tested for the
synthesis NaOH by electrolysis of NaCl (23).
Different routes have been used to prepare polyimide-based IEMs (24, 25).
Riande et al. synthesized sulfonated diamines of various chain lengths, and further
carried out condensation polymerization to synthesize a functionalized polyimide
polymer (Figure 2). The membrane was prepared by casting the sulfonated polyimide
solution in DMSO (26).
Recently, a sulfonation reaction was carried out to sulfonate PES by using concentrated
sulfuric acid as the sulfonation reagent, and CEMs were prepared from sulfonated PES
(Figure 3) and PEEK (Figure 4) by solution casting and evaporation of the solvent at an
elevated temperature (27).
Reports are available in the literature on AEMs being prepared from chloromethylated
poly(ether sulfone) (CPES) and further quaternized with tertiary amines to anchored
quaternary ammonium groups in the membrane matrix. CPES was used to prepare
AEMs by solution casting and then quaternized with aliphatic diamines of different
chain lengths (28).
Mannich reaction was used to synthesize bisphenol monomer 2,2 -dimethylamine-
methylene-4,4 -biphenol (DABP), by using 4,4,-biphenol and dimethylamine) and
formaldehyde mixture as formylating reagent. Encourage novel partially fluorinated
poly(arylene ether sulfone) was synthesized by condensation polymerization of DABP,
4,4 -biphenol, and 3,3 ,4,4 -tetrafluorodiphenylsulfone. Methyl iodide in methanol was
used to anchor pendent quaternary ammonium groups in the membrane matrix (29).
Significant efforts have been made to prepare AEMs from the engineering thermoplastic
poly (propylene oxide) (PPO). Brominated PPO was prepared by the bromination
O O
C C
O O + xnH2N R1 NH2 + (1 – x)n H2N R2 NH2
C C
O O Et3N, PhCOOH
m-Cresol
O O O O
C C C C
N N R1 N N R2
C C C C
O O x O O
1–x n
Where R1: sulfonated diamine; R2: nonsulfonated diamines
FIGURE 2 Reaction route for the synthesis of sulfonated polyimides.
O CH3 O CH3
Conc. H2SO4
S O C O S O C O
O CH3 O CH3 n
SO3H
Poly(ethersulphone) (PES) Sulphonated poly(ethersulphone) (SPES)
FIGURE 3 Reaction route for the sulfonation of poly(ether sulfone) (PES).

O O
O C O O C O
n
Poly(ether ether ketone) (PEEK)
Conc.H2SO4
O O
O C O O C O
n
SO3H
Sulphonated poly(ether ether ketone) (SPEEK)
FIGURE 4 Reaction route for the sulfonation of poly(ether ether ketone) (PEEK).
reaction using a brominating mixture to avoid the use of CME, and further different
alkyl halides were used as quaternizing reagents to anchor the basic groups in the
membrane matrix (30, 31). The reaction is shown in Figure 5.
PPO-based AEMs were prepared to separate hydrophilic anions from hydrophobic
ones. A dimethylethanolammonium group anchored onto a PPO matrix by bromination
and dimethylethanolamine (DMEA) was used to quaternize the dimethylethanolammo-
nium group present in the membrane matrix (31).
2.3 Organic–Inorganic Hybrid Ion-Exchange Membrane

Stability and durability are the most desired properties of IEMs for their use in membrane-
based electrochemical separation processes, along with their excellent physicochemical
CH3 CH3
N(CH3)3
O O
CH2Br CH2N+(CH3)3Br–
CH3 CH3
(CH3)2NCH2CH2OH
O O
CH2Br CH2N+(CH2CH2OH)Br–
(CH3)2
CH3 CH3 CH3

(CH3)2NCH2CH2OH
O O + O
N(CH3)3
CH2Br CH2 N+(CH 2CH2OH)Br CH2N+(CH3)3Br–
(CH3)2
FIGURE 5 Reactions route for the quaternization of PPO by using various aminating reagents
to prepare AEMs.
and electrochemical properties. Organic–inorganic hybrid materials are being used in aca-
demic and industrial research because of their occurrence in a single solid phase. Hybrid
materials exhibit specific chemical stability, reactivity, and flexibility to be anchored to
organo functional groups, as well as a good mechanically and thermally stable inor-
ganic backbone. Reports available in the literature show that organic–inorganic hybrid
IEMs were prepared by doping or blending inorganic fillers (acid or oxide) into an organic
polymer matrix (32–34). SPES-based hybrid CEMs were prepared from sulfonated meso-
porous silica by the infiltration method, and their stability as well as physicochemical and
electrochemical properties were dependent on the silica content in the membrane matrix
(35–39). Shahi et al. (40) developed organic–inorganic nanocomposite CEMs by the
sol–gel method. The condensation polymerization of mercaptopropylmethyl dimethoxysi-
lane (MPTMS) precursor was carried out in aqueous PVA solution in presence of trace
amounts of acid/base as a catalyst. A viscous gel was obtained at room temperature after
24 h of reaction, transformed into thin films by solution casting, and further dried at room
temperature to evaporate water. Dried films were cross-linked in solution of HCHO in
sulfuric acid at 60 ◦ C for 2 h by formal reaction, and H2 O2 was used as oxidizing reagent
for the conversion of –SH groups into acidic groups (–SO3 H) in the membrane matrix.
The reaction route for the preparation of CEMs is depicted in Figure 6.
Organic–inorganic composite AEMs based on PVA–SiO2 were prepared by the aque-
ous dispersion polymerization method. The anion-exchange groups in the membrane
matrix were introduced through the chemical grafting of 4-vinylpyridine (4-VP) with the
desired contents. The membranes were cross-linked by the formal reaction, and dimethyl
sulfate was used as quaternizing reagent to introduce the functional groups into the
membrane matrix. Physicochemical and electrochemical properties and the equivalent
pore radius of the membranes were dependent on 4-VP content in the membrane matrix.
Among the prepared membranes, those containing 25 wt% 4-VP had very good anion
selectivity and moderate membrane conductivity (41). Organic–inorganic hybrid AEMs
based on PVDF–SiO2 nanoparticles were prepared via blending. The anion-exchange
groups in the membrane matrix were introduced by the ring opening of GMA using
TMA at room temperature. Membranes of various compositions were prepared by vary-
ing the loading of SiO2 nanoparticles in the membrane matrix. It was reported that
the silica-containing membrane was more selective towards Cl− in comparison with a
membrane without silica (42). Shahi et al. prepared AESP and it was used to develop
CH CH2 CH CH2 CH CH2 CH CH2

CH2 CH2 CH2 CH2
O O O O
HS Si Si SH H2O2 HO3S Si Si SO3H

O O O O
HS Si Si SH HO3S Si Si SO3H
O O O O
CH2 CH2 CH2 CH2
H2C CH CH2 CH H2C CH CH2 CH
FIGURE 6 Schematic reaction route for the preparation of organic–inorganic nanocomposite

CEM in an aqueous medium.
novel organic–inorganic AEMs in aqueous media. AESP was synthesized via epox-
ide ring opening with an –NH2 group. In this reaction, the proton is transferred from
amine groups of APTEOS to the epoxide ring of glycidyltrimethylammonium chloride
(GDTMAC) and a secondary alcohol is formed. Then, the resultant AESP was mixed
into an aqueous solution of PVA and the pH of mixture adjusted to 2.0 by adding a
trace amount of dilute HCl solution. Further reaction was continued for 24 h at room
temperature to hydrolyze silica and effect condensation polymerization. Finally, a white
gel was obtained, which was solution-cast into thin membranes. The membranes were
dried under infrared (IR) lamps and further dried in a vacuum oven to remove the any
trace of solvent present in the membrane matrix. Formal reaction was performed to
cross-link the dry membranes. A schematic of the structure of the membrane is given in
Figure 7 (43).
2.4 Bipolar Membranes (BPMs)

BPMs are composed of cation-exchange layer (CEL) and anion-exchange layer (AEL)
and an interfacial layer (IL) between them. BPMs have gained increasing attention as
efficient tools for the production of acids and bases from their corresponding salts by
accelerated water splitting at the IL. The structure and function of a BPM is depicted
in Figure 8. The BPM is placed in a cell consisting the four compartments (catholyte,
anolyte, and compartments 1 and 2) separated by two pieces of CL and a BPM, and a
constant applied potential is applied.
Under the influence of the applied potential, ionic species (Na+ and Cl− ) are removed
and form the corresponding acid and base because or water splitting at IL. The transport
of the electrical charges through the membranes was accomplished by H+ and OH−
ions generated by the water-splitting reaction. The dissociated water is continuously
replenished from the outer phase, and thus alkaline and acidic solutions are formed on the
anion-exchange and cation-exchange side of BPM, respectively. However, the water dis-
sociation mechanism is based on a chemical reaction consisting reversible proton transfer
between the functional groups of the membrane and the water molecules at the IL.
B + H2 O BH+ + OH−
BH+ + H2 O B + H3 O+
A− + H2 O AH + OH−
AH + H2 O A− + H3 O+
In the above, B is a neutral base, BH+ is the catalytic active center (usually the
AEM’s fixed charged group), and A− is the CEM’s fixed charged group, and AH is a
neutral acid. BPMs exhibit chemical instability at high pH, poor water-splitting efficiency,
and higher membrane resistance. The aforesaid properties of BPMs were achieved by
surface treatment of commercial available BPMs followed by subsequent lamination.
BPMs were prepared by following methods: (i) adhering CEL and AEL together by
pressing with an adhesive paste under heat; (ii) casting a cation-exchange polyelectrolyte
solution onto commercially available AEMs; and (iii) simultaneous functionalization of
membrane surfaces by cation- and anion-exchange groups (44, 45). Among the above-
mentioned methods, the casting method seems to be the most attractive because of its
10
HC CH CH2 CH CH2
N+Cl−
CH2 CH CH2 n N+Cl− n
n HO
HO OH OH O O
OH HN
PVA Sol–gel:pH:2.0 HN Cross-linked CH2 CH2
+ with HCHO
O O
O O
O Si O Si O Si O
O Si O Si O Si O
O
O
O Si O O
NH NH
NH NH CH2
OH OH
NH OH OH − −
Cl+N
− −
Cl+N Cl+N
Cl+N O O
OH
−
Ci+N CH CH2 CH CH2 n
OH OH
Cross-linked organic–inorganic hybrid anion-
Anion exchange silica CH CH2 CH CH2
n exchange membrane (AEM)
precursor (AESP)
FIGURE 7 Reaction route for the preparation of anion-exchange membranes in an aqueous medium.
Interfacial layer
AEM CEM
+
H+ OH
FIGURE 8 Schematic diagram illustrating the structure and the function of a bipolar membrane
which is composed of a cation- and an anion-exchange layer with a 4- to 5-nm thick interfacial layer
arranged between two electrodes. (Please refer to the online version for the color representation of
the figure.)
simplicity and cost effectiveness. The desired properties of BPMs, such as good mechan-
ical strength, high limiting current density, high permselectivity, low potential drop,
and membrane resistance, are essential for its successful application. BPMs have been
successfully applied industrially to recover pollutants from the wastewater in chemi-
cal and food processing industries due to their ease of use, high efficiency, and low
waste production. Recent studies have reported catalytic effects of macromolecules such
as poly(ethylene glycol) (PEG), PVA, and poly(amidoamine) dendrimer-based IL on the
water-splitting efficiency of BPMs (46). Effect of the coordinated complex obtained from
the starburst dendrimer (PAMAM) and Cr3+ as the IL was studied on the water-splitting
efficiency. A membrane with higher water-splitting efficiency was obtained by solution
casting with the coordinated complex as IL (47). A heterogeneous–homogeneous com-
posite BPM was also reported by the casting method to achieve cost effectiveness, high
water-splitting efficiency, permselectivity, low resistance, salt diffusion and good stabil-
ity. Heterogeneous AELs of desired thickness were cast onto clean glass plates, and ILs
of highly sulfonated PEEK (degree of sulfonation: 80%) (SPEEK) and poly(4-VP) were
cast onto the cationic and anionic side, respectively. Finally, the CEL of SPEEK in the
same solvent was cast onto the dried surface of the IL. The fundamental characteris-
tics of BPM, such as current–voltage curves under equilibrium with NaCl and sodium
carboxylates solutions, were discussed in terms of first limiting current density (ilim1 ),
second limiting current density(ilim2 ), operating current density (iop ), and dissociation
potential (Vdis ). Water-splitting efficiency of BPM was also tested in a bipolar membrane
electrodialysis (EDBPM) cell for the conversion of NaCl or RCOONa (R: HCOO− ,
CH3 COO− , and C2 H5 COO− ) into their corresponding acids and NaOH. It was found
that the process performance (CE and recovery of RCOOH) was significantly reduced,
while energy consumption increased for converting higher homologs of RCOONa under
similar experimental conditions (48). Some commercially available bipolar membranes
(BPM) are listed in Table 2.
3 CHARACTERIZATION OF ION-EXCHANGE MEMBRANES
3.1 Spectroscopic Characterization

Spectroscopy is essentially a procedure by which the energy difference between
the allowed states of a system is measured by determining the frequencies of the
corresponding light absorbed. Organic molecules absorb radiation in discrete “packets”
of E = hν, which are also called a quantum of energy. The absorbed quantum of
energy brings about different kinds of excitation in the molecule and each requires
its own distinctive energy E . That is, each type of excitation corresponds to the
absorption of light in a different region of the electromagnetic spectrum (49). Ultraviolet
and visible light brings about movement of valence shell electrons, typically from a
filled bonding molecular orbital to an unfilled antibonding orbital. The energy needed
for this transfer lies in the range 40–300 kcal/mol. IR radiation causes vibrational
excitation of the molecular frame work of a compound (E 1–10 kcal/mol); quanta
of microwave radiation effect rotation around bonds (E ∼ 10−4 kcal/mol) and radio
waves reorient nuclear spins (E ∼ 10−6 kcal/mol), which forms the basis of nuclear
magnetic resonance spectroscopy. The vibrational excitation caused by the absorption
of the IR radiation is quantized and occurs by absorption of IR radiation energy in a
particular region of the spectrum. The position of an IR absorption band is specified in
frequency units by its wave number (v ) measured in reciprocal centimeters (cm−1 ), or
by its wavelength (λ) measured in micrometers.
3.1.1 Fourier Transform Infrared (FT-IR) Spectrophotometry. FT-IR is generally

used for the characterization of materials. An IR spectrum represents a fingerprint of
a sample with absorption peaks that correspond to the frequencies of vibrations of the
bonds between the atoms making up the material (50). In an IR spectrophotometer, poly-
chromatic IR radiation is passed through a sample of the compound and the percent
transmittance is measured. An IR spectrum is a plot of percent transmittance versus
increasing wavelength (or decreasing frequency). IR spectrum shows percent transmit-
tance versus frequency expressed as wave numbers, which have the units of reciprocal of
centimeters (cm−1 ). Each peak in the spectrum represents the absorption of IR radiation
at that frequency by the sample. A 100% transmittance means no absorption, and 0%
if all the radiation is absorbed. In the spectrum, the region from 600 to 1400 cm−1 is
called the fingerprint region because the pattern of absorption is unique to any particular
compound. The IR region constitutes three parts, namely, near IR, middle IR, and far IR.
The near-IR region corresponds to energies in the range 37–10 kcal/mol. It is of little
use because few organic compounds absorbs in this region. Radiation in the middle-IR
region (usually 4000–650 cm−1 ) has energy in the range 10−1 kcal/mol and is an impor-
tant region because most organic compounds absorb in this region. The far-IR region has
energy in the range 0.1–1.0 kcal/mol. This region is also of not much use because only
very little useful absorption occurs in this region.
3.1.2 Attenuated Total Reflection–Fourier Transform Infrared Spectroscopy (ATR-

FTIR). ATR-FT-IR spectroscopy is used to identify the types of chemical bonds or
functional groups present in membrane samples. For analysis, a sample membrane is
pressed against an internal reflection element (IRE), which may be a block of zinc
selenide or germanium (51, 52), kept under vacuum (Fig. 9). IR radiation covering a
certain frequency range (corresponding to wave numbers in the IR spectrum between
4000 and 400 cm−1 ) is focused onto the end of the IRE where the beam undergoes total
internal reflection before exiting and arriving at a detector. At each internal reflection,
the IR beam penetrates a short distance from the surface of the IRE into the sample,
forming an evanescent wave at the interface. ATR-FTIR analyses are thus based on the
interaction between the evanescent wave and any adsorbed species. ATR–FTIR is used
to characterize functional groups anchored to the membrane matrix.
3.1.3 Nuclear Magnetic Resonance (NMR) Spectroscopy. NMR is a spectroscopic

technique that relies on the magnetic properties of the atomic nucleus. When placed in
a strong magnetic field, certain nuclei resonate at a characteristic frequency in the radio
frequency range of the electromagnetic spectrum. Many atoms (1 H and 13 C) behave as if
the positively charged nucleus was spinning about an axis (Fig. 10). The spinning charge,
such as an electric current, creates a tiny magnetic field. When placed in a strong external
magnetic field, the magnetic nucleus tries to align with it like a compass needle in the
earth’s magnetic field. Because the nucleus is spinning and has angular momentum, the
torque exerted by the external field results in a circular motion called precession, just like
Polymer film
Evanescent
wave
IRE
IR radiation
incident beam
Totally internally
reflected light to detector
FIGURE 9 Schematic diagram of flow-cell operation in ATR-FTIR.
Classical
V
Bo Bo
FIGURE 10 Schematic presentation for the spinning of nucleus in a strong magnetic field.
a spinning top in the earth’s gravitational field. The rate of this precession is proportional
to the external magnetic field strength and to the strength of the nuclear magnet:
γ B0
ν0 = (1)
2π
where νo is the precession rate (the “Larmor frequency”) in hertz, γ is the strength of the
nuclear magnet (the magnetogyric ratio), and B0 is the strength of the external magnetic
field. This resonant frequency is in the radio frequency range for strong magnetic fields
and can be measured by applying a radio frequency signal to the sample and varying the
frequency until absorbance of energy is detected. 1 H and 13 C NMR spectroscopies have
been used to confirm the sulfonation of PES and characterize the prepared charged IEM.
This technique causes the change of the spin state of the nuclear magnetic moment of
the proton when the nucleus absorbs electromagnetic radiation in a strong magnetic field
(53). In 1 H NMR, the following information are obtained: Initially, it gives the relation
between the number of signals in the spectrum and the number of different kinds of
hydrogen atoms in the molecule. Thus, one can know the different kinds of environments
of the hydrogen atoms in the polymer. The area underneath each peak is proportional to
the number of hydrogen atoms causing that signal. The principal signal may get split into
smaller peaks; that is, spin–spin splitting may be observed. The type of splitting pattern
observed (doublet, triplet, quartet, and so forth) depends on the number of neighboring
nonequivalent protons. For many simple compounds, one can predict the splitting pattern
with the n + 1 rule, where n is the number of neighboring protons. Spin–spin splitting
thus helps in deducing the molecular structure. The spacing between the peaks due to
spin–spin splitting is denoted by J with units of cycles per second or hertz (Hz). J is the
coupling constant between two protons, and it gives further information on the molecular
structure and stereochemical features. Also, the 1 H NMR technique has been used to find
out the degree of sulfonation. The extent of sulfonation was estimated from 1 H NMR
spectra presented in Figure 11.
The presence of a sulfonic acid group caused a significant downfield shift from 7.37
to 7.97 ppm of the hydrogen located at the ortho position of the aromatic ring. By
evaluating the ratios between the peak area of the signal corresponding to the hydrogen
atoms located next to the sulfonic acid groups (HE ) and the peak areas of the signals
corresponding to the other aromatic hydrogen atoms (HA, A B ,B ,C ,D ), and with 6 − 2α the
HB
HC
HE
HA
HD
0.00 7.80 7.60 7.40 7.20 7.00 6.80

Chemical shift (ppm)
1
FIGURE 11 H NMR of sulfonated poly(ether sulfone).
number of residual hydrogen atoms (HA,A B ,B ,C ,D ), the degree of sulfonation of SPES

was estimated using following mathematical expressions:
α AHE
= (2)
6−2α AHA,A ,B ,B ,C ,D
AHE
z= (3)
AHA,A ,B ,B ,C ,D
and
6z
x= × 100 (4)
1/2z

where x is the degree of sulfonation (mol%), AHE is integral of HE , and HA, A B ,B ,C ,D
is integral of HA, A B ,B ,C ,D . From Equation 4, it was found that the degree of sulfonation
for PES under given experimental conditions was 61.00% and that it varied with the time
and temperature of the sulfonation.
3.1.4 Electrochemical Impedance Spectroscopy (EIS). It is a powerful technique for

studying the electrical properties of materials and is used to characterize a wide variety
of electrochemical phenomena in porous materials, solids, liquid electrolytes, as well
as synthetic and biological membranes (54). In general, this method provides a lot of
information on the functional and structural characteristics of membranes. It works on the
principle that the translation of the electrochemical system for the IEMs to an equivalent
electrical circuit consist of capacitors and resistors. An alternating sinusoidal current I (t)
or voltage (depending on the condition) of a given frequency and amplitude is applied
to the system, and the response of the system is monitored regularly. The resulting
voltage drop over the system is measured as a function of time U (t), and the phase
shift (ϕ) relative to the input signal is determined. This procedure is repeated at different
frequencies, and the impedance (Z ) can calculated in accordance with Ohm’s law as
U (t)
Z = (5)
I (t)
where, U (t) is the voltage as a function of time t (in volts) and I (t) is the current as a
function of time t (in amperes). In the equivalent electrical circuit, the single IEM can be
easily represented as a simple resistor. The applied current produces a voltage drop over
the membrane under investigation, which can be translated into a membrane resistance
(this is comparable to the resistance of the resistor in the electrical circuit). In principle,
this resistance represents the resistance of the membrane containing also the solution
resistance (RM+S ), but the pure membrane resistance (RM ) can be easily obtained by
subtracting the solution resistance (RS ) as determined from a blank measurement without
the membrane. When the frequency is decreased, the contribution of the interfacial ionic
charge transfer from the solution phase through the electric double layer to the membrane
can be obtained. Ions start to migrate through the interfacial double layers, and a phase
shift is observed. The resistance (RDL ) and capacitance (C ) of ionic transport through
these double layers become visible. This surface charging is similar to what is observed
for a capacitor, and the interfacial ionic charge transfer through the double layer is
represented in the equivalent circuit model as a resistor and capacitor in parallel. When
a very low frequency signal (current) is applied, in addition to the membrane and the
ionic transfer through the electrical double layer, concentration gradients in the diffusion
boundary layers adjacent to the membrane become visible. The phase shift and phase
angle at each specific frequency give the overall response of the different phenomena
in the system sensitive to that specific frequency. Complex systems often give rise to
nonideal responses. In these cases, Q, which represents a nonideal capacitor, can be
considered to obtain a better fit (55). The diffusion boundary layer can be represented
by a resistor and a constant phase element Q connected in parallel, where the constant
phase element represents the nonideal capacitive behavior of the diffusion boundary layer.
The different contributions of IEM and the solution to the resistance can be electrically
represented by the equivalent circuit model as presented in Figure 12 (56, 57).
3.1.5 Thermal Analysis of Ion-Exchange Membranes. The term thermal analysis

(TA) is frequently used to describe analytical experimental techniques that investigate
the behavior of a sample as a function of temperature. It refers to the conventional TA
techniques such as thermal gravimetric analysis (TGA), differential scanning calorimetry
(DSC), and dynamic mechanical analysis (DMA). The advantages of TA over other
analytical techniques are (i) the sample can be studied over a wide temperature range
using various temperature programs; (ii) almost any physical form of sample (solid,
liquid, or gel) can be accommodated using a variety of sample vessels or attachments;
(iii) a small amount of sample only (0.1 μg–10 mg) is required; (iv) the atmosphere
in the vicinity of the sample can be standardized; (v) the time required to complete
an experiment ranges from several minutes to several hours; and (vi) TA instruments
are reasonably priced. In polymer science, the sample transition temperatures and
decomposition characteristics are routinely performed using TA techniques before
spectroscopic characterization.
3.1.6 Thermal Gravimetric Analysis (TGA). TGA is a simple analytical technique

that measures the weight loss of a material as a function of temperature. It is used
to characterize polymeric materials, by determining the change in weight in relation
to change in temperature and thermal stability of the polymeric membranes. When the
materials are heated, they can lose weight from drying or as a result of chemical reactions
that liberate gases. Some materials can gain weight by reacting with the atmosphere in the
testing environment. Since weight loss and gain are disruptive processes to the sample
material or batch. Knowledge of the magnitude and temperature range of reactions is
necessary in order to design adequate thermal ramps and holds during critical reaction
periods. The measurement is normally carried out in air or in an inert atmosphere using
helium or argon, and the weight loss is recorded as a function of varying temperature in
Rα RDBL
RM+S
C Q
Membrane +
solution
Electrical Diffusion
double layer boundary
layer
FIGURE 12 Equivalent circuit for the ion-exchange membrane with solution.

A
B
Weight loss (%)
C
Temperature (°C)
FIGURE 13 Schematic representation of a TGA curve for a membrane.
a dynamic mode of operation. A representative of TGA curve for a membrane is shown

in Figure 13.
As many weight loss stage occur during the TGA of the samples, the weight loss
curve may require transformation before results can be interpreted. A derivative weight
loss curve of TGA can be used to tell the point at which weight loss is most apparent.
It is essentially a quantitative and an extremely powerful thermal technique but does
not provide the direct chemical information. It has the ability to generate fundamental
quantitative data from any types of material. The various pieces of information that are
obtained from a TGA curve are given below:
1. Thermal Stability. Related materials can be compared at elevated temperatures

under the required atmosphere. The TGA curve can help to elucidate decomposition
mechanisms.
2. Kinetic Studies. A variety of methods exist for analyzing the kinetic features of all
types of weight loss or gain, either for predictive studies or for understanding the
controlling chemistry.
3. Material Characterization. TGA and differential thermal gravimetric (DTG) curves
can be used to “fingerprint” materials for identification or quality control.
4. Corrosion Studies. TGA provides an excellent means of studying oxidation or
reaction with other reactive gases or vapors.
5. Simulation of Industrial Processes. The thermobalance furnace may be thought of
as a minireactor, with the ability to mimic the conditions in some types of industrial
reactors.
6. Compositional analysis. By a careful choice of temperature programming and
gaseous environment, many complex materials or mixtures may be analyzed by
selectively decomposing or removing their components. This approach is regu-
larly used to analyse, for example, the filler content in polymers, carbon black in
oils, ash and carbon in coals, and the moisture content of many substances. TGA
(Mettler Toledo TGA/SDTA851e with stare software) under nitrogen atmosphere

at the heating rate of 10 ◦ C min−1 from 50 to 600 ◦ C was employed to assess the
degradation process and the thermal stability of the prepared membranes.
3.1.7 Differential Scanning Calorimetry (DSC). DSC is an effective analytical tool

for characterizing the physical properties of a polymer. DSC enables the determination
of melting, crystallization, and mesomorphic transition temperatures; the correspond-
ing enthalpy and entropy changes; and characterization of the glass transition and other
effects that show changes either in heat capacity or latent heat. Calorimetry takes a
special place among the characterization methods. In addition to its simplicity and uni-
versality, the energy characteristics (heat capacity CP and its integral over temperature
T , i.e., enthalpy H ) measured via calorimetry have clear physical meanings even though
sometimes the interpretation may be difficult. DSC is widely used in industrial settings
as a quality control instrument because of its applicability in evaluating the sample purity
and for studying polymer curing. These measurements provide quantitative and quali-
tative information about physical and chemical changes that involve endothermic and
exothermic process and change in heat capacity. DSC has proven to be a very reliable
technique to obtain heat capacity at elevated temperatures in a reasonable time. DSC also
enables the study of the kinetics of transitions over a wide dynamic range. Because of its
simplicity and ease of use, DSC is widely applied in polymer science (58). Differential
scanning calorimeters commonly have two sample positions, one for the sample under
investigation, and the other for a reference sample which is often an empty crucible or one
filled with an inert material. In systems such as used in most heat flow DSCs and ultrafast
scanning calorimeters, the sample may exchange heat directly with the surrounding oven
which is not measured by the heat flow sensor. The heat flow rate not measured by the
sensor may reach up to 50% of the total heat flow rate exchanged. Assuming the same
losses for sample and reference sides, and, more importantly, that they are not changing
between calibration runs and the measurement, these losses can be theoretically included
in the calibration function. The schematic of a typical DSC curve is shown in Figure 14.
From the DSC measurements, various pieces of information can be obtained, such as the
glass-transition temperature (Tg ), amorphous nature, and the degree of crystallinity of
polymeric materials. Mettler Toledo DSC822e thermal analyzer with stare software was
used to record the DSC thermogram of the developed membranes.
3.1.8 Dynamic Mechanical Analysis (DMA). DMA is a useful technique for observing
the viscoelastic nature of polymers. When a polymer is subjected to forced mechanical
vibration at a fixed frequency, temperature, and elongation, a fraction of the energy is
absorbed (59). It is used to understand the mechanical stability of polymeric materi-
als (membranes). Polymers exist in two distinct states, namely, the glassy state (high
modulus) at low temperatures, and rubbery state (low modulus) at higher temperatures.
The change in the glass transition or alpha relaxation can be observed by scanning the
temperature during a DMA experiment (Fig. 15). It is also used to investigate the fre-
quency (and therefore time) dependent nature of the transition and provides the Young’s
modulus. DMA instrument consists of a displacement sensor such as a linear variable
differential transformer, which measures a change in voltage as a result of the instrument
probe moving through a magnetic core, a temperature control system or furnace, a drive
motor (a linear motor for probe loading which provides load for the applied force), a
Exo
Endo
Tg
Temperature (°C)
FIGURE 14 Schematic representation of DSC curve for a membrane.
800
700 Glassy
plateau
600
500
Glass transition region
Modulus
400
Leathery
300 region
200
100
Rubbery plateu
0
–100
50 100 150 200 250 300
Temp. (°C)
FIGURE 15 Dynamic mechanical analysis of different hybrid nanofiltration (NF) membranes.

Source: Taken from Reference 60.
drive shaft support, a guidance system to act as a guide for the force from the motor to
the sample, and sample clamps to hold the sample being tested.
3.2 Physicochemical Characterization of the Ion-Exchanged Membranes

The highly charged membrane, CEMs in which the fixed negative charges are in equi-
librium with mobile cations in the interstices of the polymer membrane matrix mobile
cations. The mobile cations are referred to as co-ions and are more or less completely
excluded from the polymer membrane as a result of Donnan exclusion (61). AEMs carry
fixed positive charges that mainly allow the transfer of anions through the polymer mem-
brane matrix. The properties of the highly charged membranes are mainly dependent on
the density of polymer network, the hydrophobic or hydrophilic nature of the membrane
matrix, and the type and concentration of the fixed charges in the polymer matrix. The
extent of co-ions excluded from the charged membranes depends not only on membrane
properties but also on the ionic concentration of the feed solution. High permselectivity,
low membrane resistance, and good mechanical, chemical, and thermal stabilities are
most desired properties for good highly charged membranes. These properties can be
determined from the basic material used for the preparation of membranes and fixed
charge concentrations. The basic material determines to a large extent the mechanical,
chemical, and thermal stability of the membranes. The type and concentration of fixed
charges nnot only determine the permselectivity of the membranes but also influence the
mechanical and swelling properties, respectively.
3.2.1 Determination of Water Uptake. The swelling capacity of a highly charged mem-
brane not only determines dimensional stability but also affects its selectivity, resistance,
and water transport number. It depends on the nature of the polymeric material, the ion-
exchange capacity, and the cross-linking density. Usually, the swelling of a membrane is
expressed in terms of water uptake (ϕw ) under given experimental conditions. The water
uptake is evaluated from the difference in weight before and after complete dryness of
the membranes. The membrane is immersed in distilled water (DW) for 24 h and its
wet weight is recorded after complete removal of surface water by an absorbing paper.
Weight of dry membrane is recorded for the dried membrane sample (under vacuum at
60 ◦ C for 10 h) until a constant weight is obtained. It can be calculated by using the
expression:
(Wh − Wd )
φw = (6)
Wd
where, Wh is the wet membrane weight, and Wd is the dry membrane weight. The water
content in terms of the volume fraction of water in the membrane matrix is determined
by following equation:
w
dw
φw = wd (7)
w
dw + dp
where w is the weight difference between the wet and dry membrane, and dw and dp
are the densities of water and dry membrane, respectively (1, 35).
3.2.2 Determination of Ion-Exchange Capacity (IEC). IEC is defined as the ratio

between number of exchangeable ionic groups (equivalents) and the weight of dry mem-
brane. For the estimation of IEC of a CEM, a piece of membrane is equilibrated in 1.0 M
HCl to convert it into the H+ form and the excess acid is removed by washing with DW.
The washed membrane is then equilibrated in 50 ml of 0.50 M NaCl solution to exchange
H+ by Na+ . The amount of H+ ions liberated in solution was determined by acid–base
titration (62). The IEC of the AEM is determined using the Mohr method, in which the
membrane in the chloride form is converted into the sulfate form by immersing it in an
aqueous Na2 SO4 solution (0.50 M) for 8 h. The chloride ions released from the membrane
are titrated with aqueous AgNO3 solution (0.10 M). The IEC values are calculated from
the released chloride ions and expressed as milliequivalent per gram of dry membrane
(Cl− form) (35).
3.2.3 Surface Charge Concentration. The surface charge density of the membranes
in units of (moles of sites)/(unit volume of wet membrane) is calculated by using the
following equation:
τ (IEC)ρd
χm = (8)
V
where the membrane porosity τ (volume of free water within the membrane per unit
volume of wet membrane) can be obtained by
V
τ= (9)
1 + V
In the above, V is the change in the volume of the membrane because of water per
unit of dry membrane, estimated by
wdp
V = (10)
dw wd
3.2.4 Dimensional and Oxidative Stability. Membrane stability and durability are very
important parameters for the use of highly charged membranes in the electromembrane
process. The stability of the polymer electrolyte membranes in Fenton’s reagent (solution
containing H2 O2 and transition-metal ions) has been recognized as an important indi-
cation of the durability of the membranes (63). The degradation of the highly charged
membranes is tested in Fenton’s reagent (Fe2+ –H2 O2 ) for 1 h at 70 ◦ C. The formation
of • OH and • OOH radicals takes place after the decomposition of H2 O2 , which in turn
attack the hydrogen bonds in the membranes matrix. The life time of • OH or • OOH
radicals is very short. Peroxy free radical attack is more efficient at higher temperature
and occurs in the proximity of hydrophilic domains. The degradation of the membranes
is evaluated by weight loss, loss in IEC, and visual observation.
3.3 Electrochemical Characterization

The knowledge on the electrochemical properties such as counterion transport number,
permselectivity, electroosmotic stability, and membrane conductivity under actual oper-
ating environment is essential to assess the suitability of the developed membranes for
use in EMPs.
3.3.1 Membrane Potential Measurements. It is observed that when a membrane sep-

arates two electrolyte solutions, an electric field (diffusion potential) maintains elec-
troneutrality and brings about the balance of fluxes. The magnitude and sign of potential
depend on the nature of the membrane and the permeating species. If the membrane
carries no fixed charges, the potential is the same as the liquid junction potential while
the membrane carries some fixed charges; the magnitude of the potential is determined
by the concentration of the external solution, and its sign by the nature of the fixed
charge. However, it is found that some of the membranes are completely inert due to the
absence of a measurable quantity of fixed charge, but they have a tendency to generate
an electric potential. This is attributed to the adsorption of cations or anions to make
them anion or cation selective. The electrical potential arising across an ionic membrane
separating different salt solutions are usually measured by constructing cells of the type
as presented in Figure 16.
The reference electrode may be a reversible electrode of the type Ag–AgCl standing
in a chloride solution or calomel connected to the solutions via KCl–agar salt bridges. In
the former case, the total potential measured is made up of two compartments, namely,
the electrode potential and the the membrane potential. In the latter case, the cell potential
directly gives the membrane potential. These measurements to evaluate membrane poten-
tial are not unambiguous (64, 65). These types of measurements have become routine to
characterize the selectivity of membranes. The total membrane potential is considered to
be composed of two Donnan potentials at the two solution–membrane interfaces 1 and
2 and a diffusion potential arising from the unequal concentration of the two membrane
faces. The membrane surfaces are assumed to be in a state of equilibrium instantaneously
established, although this seems less true as the concentration gradient and the conse-
quent steady diffusion of the electrolyte and solvent become appreciable. The detailed
experimental setup used for membrane potential measurements is shown in Figure 17.
Reference Solution 1 Membrane Solution 2 Reference

electrode electrode
Electrode potential Electrode potential
Donnan Donnan
potential potential
Diffusion
potential
FIGURE 16 Schematic diagram for membrane potential measurements.
0.1 M 0.01 M
NaCl mV NaCl
IEM
Calomel
Stirrer
electrode
FIGURE 17 Schematic experimental setup for the determination of membrane permselectivity

by membrane potential.
Membrane potential data are used to calculate the counter-ion transport number using
Equation 11 by Teorell, Meyer, and Sievers (TMS) approach (62):
RT a1
E m = (1−2tim ) ln (11)
nF a2
where E m is the potential difference between two solutions containing the electrolyte, n
is electrovalence of electrolyte, tim is the transport number, α1 and α2 are the activities
of the electrolyte solutions, R is the gas constant, T is temperature, and F is the Faraday
constant. The superscript ‘m’ refers to the membrane (8).
The counterion transport number is also calculated by Hittorf’s method. The experi-
mental cell used for the determination of transport number has two asymmetric compart-
ments separated by a circular membrane (7.0 cm2 ) and electrodes (Fig. 18).
The cathodic and anodic compartment capacity is 200 and 20 ml, respectively. The
electrodes, obtained from Titanium Tantalum Products, are made of an expanded TiO2
sheet coated with three precious metal oxides (titanium, ruthenium, and platinum)
(6.0 μm thickness), with 1.5 mm thickness and 25.0 cm2 area. The distance between
the electrodes and the effective membrane area was 0.11 cm and 25.0 cm2 , respectively.
Peristaltic pumps were used to feed NaCl solution (0.10 M) in a recirculation mode into
the cathodic compartments and DW into the anodic compartment at constant flow rate.
In order to control both the current intensity and the voltage, a digital multimeter was
placed in series to apply a current across the electrodes. The applied current density
was 8.0 mA/cm2 . Experiments were carried out for 1 h, and the samples were taken out
from the anodic and cathodic compartments to determine the Cl− ion concentration.
The counter-ion transport number (Cl− ) was determined using the following equation:
nF 0 0
t−m = (C V − C − V − ) (12)
It
where n is the charge on chloride ion (Cl− ), F is the Faraday constant, I is the applied
current, and t is the time. C 0 and C − are the initial and final concentration of Cl− in
IEM
− +
200 ml 20 ml
0.1 M NaCl
Water
Pump B Pump A
FIGURE 18 Schematic diagram of the experimental setup for the determination of the counterion
transport number by Hittorf’s method.
the anodic compartment, and V 0 and V − are the initial and final volume of the anodic
compartment. Similarly, the cation transport number was determined using the following
equation:
nF 0 0
t−m = (C V − C + V + ) (13)
It
where n is the charge on Na+ , F is the Faraday constant, I is the applied current, and
t is the time. C 0 and C+ are the initial and final concentration of Na+ in the anodic
compartment, and V 0 and V + are the initial and final volume of anodic compartment.
3.3.2 Membrane Permselectivity Measurements. It is an important parameter that

determines the performance of a membrane in a membrane-based electrochemical
process. It describes the degree to which a membrane passes counter-ions and retains the
co-ions of the opposite charges. The permselectivity of the highly charged membranes
(CEMs and AEMs) is calculated by using Equations 14 and 15.
The membrane permselectivity towards the cations was estimated with the help of
transport number using
t m − t+
Ps = + (14)
1 − t+
Similarly, the membrane permselectivity towards the anions was estimated with the
help of transport number using the equation
t−m − t−
Ps = (15)
1 − t−
where t+ and t− are the counterion (cation and anion) transport numbers in the solution,
t+m and t−m are the counter-ion (cation and anion) transport numbers in the membrane
phase, and P+ and P− are the CEM and AEM permselectivity, respectively.
3.3.3 Electroosmotic Permeability Measurements. If an electric field is applied to the

charged surface, force is exerted on both solutions part of double layer and the charged
surface. At the immobile surface, the solution part of the double layer will respond to
shear, and the part close to the surface will remain stationary, but the remaining part
of the solution will move under the influence of the field carrying the solvent with it.
This process is called electroosmosis. The solvent is transported either by an association
with the transported ion, such as hydration sphere, or by hydrodynamic pumping due to
the movement of the ions and the associated solvent molecules. This solvent transport
accompanying the ion transport through the membrane is termed electroosmosis. The
application of an electric field to a membrane causes not only transport of ions but
also transport of liquid existing in the pores of the membrane (66). This solvent transport
occurs as a result of the solvation of ions through the membrane under an applied potential
can be called, in a phenomenological way, electroosmosis. Usually, this transport takes
place in the direction in which the counter-ions moves. As counter-ions experience less
resistance due to solvent movement, also in the same direction, they move faster than
the co-ions. True transport numbers of counter-ions account for increased ion transport
due to convection. Electroosmotic permeability for different membranes was measured
in a two-compartment membrane cell with an effective membrane area of 20 cm2 , under
equilibration of 0.01 M NaCl solutions. Both compartments were kept under constant
Motor Motor
Capillary
– +
Oar Membrane
FIGURE 19 Schematic diagram of the experimental setup for electroosmotic study.
agitation by means of a mechanical stirrer (Fig. 19). A known potential was applied
across the membrane using Ag/AgCl electrodes, and, subsequently, the volume flux was
measured by observing the movement of liquid in a horizontally fixed capillary tube of
known radius.
The current flowing through the system was also recorded with the help of a digi-
tal multimeter. Several experiments were performed to obtain reproducible values. The
electroosmotic permeability of membrane can be defined as

J
= L12 (16)
I
where L12 is electroosmotic permeability of the charged membranes (A−1 cm s−1 ), J

is the pure water flux (l/m2 /h), and E is the applied potential gradient across the
membrane. The water dragged by the cations crossing the IEM from the anode to the
cathode was determined from the displacement of the liquid in the horizontal fixed
capillary of known radius in the cathodic compartment. The change in volume in the
cathodic compartment, V , arising from the transport of Q coulombs of electricity
across the membranes, is related to observed volume, V0 (67, 68) as
Q
V = V0 + (V − VAg − t+ V MCl ) (17)
F AgCl
where V MCl and t+ are the partial molar volume of the electrolyte and the cation transport
number in the solution, respectively. The water transport number tw0 in moles of water
per faraday is given by expression
F V Fμ
tw0 = = (18)
Q Vw 18
where V w is the partial molar volume of water (18 cm3 /mol) and μ is the volume of
water flowing per coulomb (V /Q) from the anode to the cathode.
3.3.4 Membrane Conductivity Measurements. Conductivity is related to the electrical

resistance of highly charged membranes and is one of the factors that determine the
energy consumed in the electromembrane processes. It may be noted that true electrical
resistance is measured by AC or electrochemical impedance at a certain frequency. In
most practical cases, however, it is considerably lower than the resistance of the dilute
solutions, since the ion concentration in the membrane is relatively high. The specific
membrane resistance is given as /cm. From the engineering point of view, the membrane
area resistance in cm2 is more convenient. The membrane resistance was measured
with the help of the cell and impedance spectroscopy method. The cell was composed
of two black graphite electrodes fixed on Plexiglas plates with known active area as
well as membrane (69). The electrodes were not in direct contact with membrane. The
membrane resistance (R m ) was estimated by subtracting of electrolyte resistance (Rsol )
without membrane from the membrane resistance equilibrated in electrolyte solutions
(Rcell )[R m = Rcell − Rsol ]. In another set of experiments, the membranes were sandwiched
between two homemade stainless steel circular electrodes (4.0 cm2 ). Direct current (dc)
and sinusoidal alternating currents (ac) were supplied to the respective electrodes for
recording the frequency at a scanning rate of 1 μA/s within a frequency range of 1–106
Hz (70). The spectrum of the blank short-circuited cell was also collected and this data
was subtracted (as a series circuit) from each of the recorded spectra of the membranes
to eliminate cell and wiring resistances and inductances.
As usual, the results were interpreted in terms of an electric circuit made up of
a resistance, R0 , which accounts for the protonic resistance of the membrane, in series
with a parallel RC circuit accounting for the membrane–electrode polarization processes.
The complex impedance of the circuit is given by
R
Z ∗ = R0 + (19)
1 + jRωC
where ω is the angular frequency. The plot Z versus Z , called the Nyquist diagram,
is a semicircle whose high frequency side intersects the abscissa axis at Z ∗ = R0 . In
fact, Z → R0 when ω → ∞ while Z → R0 + R when ω → 0. An alternative method
to determine R0 is the Bode diagram where both the modulus of the complex impedance
|Z ∗ | and the phase-out angle ϕ [= tan−1 (Z /Z )] are plotted against log f . The modulus
of the real component of the impedance at the frequency f at which ϕ = 0 is taken as the
protonic resistance R0 of the membrane. The corrected spectra were viewed as complex
impedance plots, with the imaginary component Z on the y-axis and the real component
Z on the x -axis (Z = Z − iZ ); the ionic resistance of each membrane was estimated
to be the intersection of the x -axis with the extrapolation of the low frequency linear
component of each plot.
The membrane resistances were obtained from Nyquist plots (Fig. 20) by using the
“fit and simulation” method, and the effective membrane resistance, determined experi-
mentally as a function of solution concentration in equilibrium with the membrane, could
be used for the estimation of membrane specific conductivity. The specific conductivity
κ m of the membrane in given by the equation 20.
x
κm = (20)
AR m
where x is the thickness of the wet membrane, A is area, and 1/R m is its electrical
conductivity.
45
35 CEM
AEM
Z″ (ohm) 25
15
–5
0 10 20 30 40
Z′ (ohm)
FIGURE 20 Nyquist plot for cation and anion exchange membrane (CEM and AEM) in equi-
librium with 0.10 M NaCl solutions. (Please refer to the online version for the color representation
of the figure.)
4 ELECTROMEMBRANE PROCESSES BASED ON IEMs
4.1 General Description and Application of ED

ED is an IEM (CEM and AEM) based separation process in which membranes are
arranged in alternative, repeating unit to achieve the desalination or separation of inor-
ganic components from organic ones. An ED cell consists of diluted compartments (DCs)
and concentrated compartments (CCs) along with electrode wash (EW, (Na2 SO4 ) solu-
tion) compartments (Fig. 21).
If an electrolyte solution is pumped through these cells and an electrical potential
between the electrodes is established, the cations migrate towards the cathode. They
pass through the CEM but they are retained by the AEM. Likewise, the anions migrate
towards the anode and pass through the AEM but are retained by the CEM. The overall
result is that an electrolyte, that is, a salt or an acid or a base, is concentrated in alternate
compartments while the other solutions are depleted of ionic components. A CEM, a cell
containing the concentrate, an AEM, and a cell containing dilute constitute a cell pair.
In an industrial size ED stack, 100–200 cell pairs are arranged between the electrodes.
Electrode reactions take place in the electrode compartment as given below:
At the cathode, 2e− + 2H2 O = H2 (g) + 2OH−

At the anode, H2 O = 2H+ + 12 O2 (g) + 2e− or 2Cl− = Cl2 (g) + 2e−
Small amounts of hydrogen and chlorine are generated in ED process. To avoid gen-
eration Cl2 gas and make the medium (EW) conducting, a dilute solution of Na2 SO4
(0.1 M) is generally recirculated through electrode compartments.
ED is used for the production of portable water from blackish water via desalination.
It has flow of unidirectional current their cause specific problem is generated by blackish
Diluted compartment (DC) Concentrated compartment (DC)
EW
EW
Cathode Anode
EW EW
Feed solution
Cation Anion-exchange membrane

Anion Cation-exchange membrane
FIGURE 21 Schematic representation of the principle of electrodialysis. (Please refer to the

online version for the color representation of the figure.)
water. Blackish water with high sulfate content, heavy metals, and organic materials
settle down on the IEM, causing fouling and reduced efficiency of operation due to
scale formation on the concentration chambers, which results in low water recovery
and disposal of the concentrated stream in large volumes. For the controlling fouling,
changing the membrane surface from the concentrate side to the dilute chamber side
was found effective, which improved the ED efficiency. The usefulness of this concept
emerged as electrodialysis reversal (EDR) and was proved in the late 1960s. According to
this concept, the polarity of electrode is changed 2–5 times per hour for reducing fouling.
When the polarity is reversed, chemical reactions at the electrodes are reversed. EDR
reduces the fouling tendencies of water by reversing the polarity of the electrodes every
15–20 min. This change in polarity causes the scales to dissociate from the membranes.
EDR technology is applied to the production of drinking water, industrial water, and
wastewater reuse projects. Municipalities have found EDR successful for the removal of
radium, arsenic, and per chlorate, as well as desalination of well and surface waters.
4.1.1 Electrochemical Process for Water Purification.
4.1.1.1 Electrochemical Process for Recovery of Toxic Metal from Wastewater. In recent
years, ED has been successfully used as promising technology for separation and recovery
of heavy metal ions (Cd, Zn, Pb, Cu, Ni, Zn, Mn, and Fe) from electrochemical plating
baths and industry wastes (71–76). Rahman et al. have developed an integrated process
for metal ion recovery from metal-containing wastewater by ED, as shown in Figure 22.
It consist an alternating arrangement of AEMs and CEMs along with electrode wash
streams. Metal-containing wastewater is fed into diluted stream (DS) while DW is fed
into concentration stream (CS). Under the influence of applied electrical gradients, metal
Treated water
EW 5
EW
Cathode 1 Anode
4
2
3
EW
EW
Sludge
Feed water
Cation Anion-exchange membrane

Anion Cation-exchange membrane
FIGURE 22 Schematic presentation of an electrodialysis cell for metal ion recovery from
wastewater. (Please refer to the online version for the color representation of the figure.)
ions diffuse through CEMs and their respective anions through AEMs. Metal ion con-
centration in the DS depleted while it increased in CS and finally reduced to few ppm
(from 1000 ppm) in wastewater (75). Shahi et al. modified IEMs (CEM and AEM) and
used them in ED for salt separation. The rate of salt separation changed after modifica-
tion of membranes and followed the trend, NaCl > CaCl2 > MgCl2 > CuCl2 . Membrane
selectivity increased towards monovalent ion because the PPY layer on the membrane
surface hindered the migration of bulkier ions through membranes (77). Shahi et al. sep-
arated monovalent and bivalent ions with the help of ED, and the separation trend was in
the order Cu2+ > Mg2+ > Ca2+ (78). Monovalent cation-selective membranes (MCSMs)
were prepared by the sol–gel method in an acidic medium, and –SO3 H groups were
anchored at inorganic segment by oxidation of –SH groups with H2 O2 as oxidizing
agent. The membranes were physicochemically and electrochemically characterized. The
electrotransport efficiency (η) of MCSMs for different cations was obtained from the
change in concentration after passage of the desired coulombs of electric charge (40).
η of MCSMs, especially MCSM (Si-65%), for cations was found to be in the order
Na+ > Ca2+ > Mg2+ > Fe3+ . The separation of Na+ and Mn+ was carried out in a three-
compartment ED cell by taking the mixed electrolyte solution of equal concentration. On
the basis of η of MCSM for individual cations (Mn+ , Na+ , Ca2+ , Mg2+ , Fe3+ ), a sep-
aration factor (SF) was estimated from the flux ratio of ηNa+ and ηMn+ (40). Relevant
data for MCSM (Si-65%) and Nafion 117 membranes are presented in Figure 23.
It was revealed that SF for Na+ /Mn+ was high, especially in case of the Na+ /Fe3+
mixture (40). Amado et al. modified chitosan containing –PO3 H2 or –N+ (CH3 )3 Cl−
group and further blended in PVA for the separation of metal ions. The relative per-
meability of composite membranes for various cations was found to be in the order
Na+ > Ca2+ > Mg2+ (79).
4.1.1.2 Separation and Recovery of Anions from Wastewater. The NO− 3 concentration
in ground water is growing day by day due to the excessive use of fertilizers as well as
to the discharge of human wastes and industrial wastewater. According to the US Envi-
ronmental Protection Agency (EPA), the maximum permissible limit of NO− 3 in drinking
water is 45 mg/l, while European community has recommended a value of 25 mg/l.
NO− 3 -contaminated water may cause methemoglobinemia in humans, and nitrosamines
10
Si-65%
8 Nafion
Separation factor
6
0
Na+/Ca2+ Na+/Mg2+ Na+/Fe3+
Electrolyte mixed system
FIGURE 23 Separation factor of Si-65% and Nafion 117 membranes for different mixed elec-
trolyte solutions (0.01 M).
(by-products) derived from NO− 3 are carcinogenic (80). Thus, it is important to urgently
develop a process for the separation and removal of NO− 3 from drinking and wastewater
to protect public health and the environment. Several reports are available in the literature
for the separation and recovery of NO− 3 from drinking and wastewater by ED (81, 82).
Fluoride is both beneficial and harmful to public health depending on its concentration
in drinking water. More than 1.0 mg/l fluoride concentration leads to bone diseases, teeth
mottling, lesions of endocrine glands, thyroids, liver, as well as other organs of human
body. The World Health Organization has recommended 1.0 mg/l as the maximum per-
missible limit of fluoride in drinking water. There has been increasing interest to use
ED for the treatment of fluoride-rich water, because it is simple and avoids the use of
chemical processes (83, 84). Arar et al. (85) separated and recovered F− from wastewater
by ED in the presence of interfering ions (SO4 2− /Cl− ).
The perchlorate ion (ClO− 4 ) is an emerging contaminant in water and has received
much attention among public and private sectors. Thus, there is an urgency to develop
innovative processes for separation and removal of ClO− 4 from contaminated wastewater.
Wang et al. have developed an ED-assisted catalytic reduction (EDACR) process for
ClO− −
4 removal from dilute waste solution. They could remove 88% ClO4 from synthetic
wastewater and the developed process could be used for the separation and recovery of
ClO− 4 from synthetic solutions in the low concentration range (10–100 ppm) as well (86).
4.1.1.3 Electro-Electrodialysis (EED) for Chromic Acid Recovery from Wastewater. An

EMP based on electro-electrodialysis (EED) principles offers many advantages in achiev-
ing in situ ion substitution and separation in different electrochemical transformations.
This is a combination of membrane electrolysis (ME), ion transport across charged IEMs
(CEMs and AEMs), and electrochemical reactions occur at electrodes. During water
electrolysis, the following reactions occur at anode and cathode (4):
At the anode, 1
2 H2 O → 14 O2 + H+ + e−
At the cathode, H2 O + e− → 12 H2 + OH−
Thus, electrode reactions provide H+ and OH− for in situ ion substitution, and the
whole reaction is known as water splitting. This process has been successfully used
for chromic acid recovery, electrochemical transformation of valuable salts into their
corresponding acids and bases, and production of pharmaceutical-grade organic acids
from their salts.
Shahi et al. developed EED based on an electromembrane reactor (EMR) for in situ
substitution, separation, and recovery of chromic acid and heavy metal ions from synthetic
individual or mixed solutions of chromate and metal electrolyte solutions. A single-step
electrotransport and in situ ion substitution of Cr(VI) was carried out in an EMR. Two
steps occurred in this process: (i) electrotransport of CrO4 2− from the central compart-
ment (CC) to anolyte took place across the AEM, while metal ion was transferred from
CC to catholyte across the CEM under the influence of applied electrical gradient, and
(ii) in situ ion substitution, in which chromic acid was formed by the combination of
H+ and CrO4 2− while metal hydroxide was formed in catholyte by the combination of
OH− and the metal ion. In this process, the combined effect of electrode polarization
and electromigration of CrO4 2− occurred, while the metal ions migrated towards the
anode and cathode, respectively. Results have revealed that the developed EMR will be
an efficient tool for the separation and recovery of chromic acid from wastewater from
the electroplating industry (4).
4.1.1.4 Electrodeionization (EDI) for Ultrapure Water. Electrodeionization (EDI) is a

membrane-based separation process that removes ions from water and produce ultrapure
water (8.0–18.2 M conductivity). EDI is an advantageous process because of stable
product quality and also because there is no need to use an acid or base for resin
regeneration. It is a continuous chemical-free deionization process and is based on the
EED principle and mixed bed of IER. The EDI cell consist DC, CC, and electrode
compartments (Fig. 24).
Feed
1/4 O2 + H+ + e–
Na+ Cl–
Enhanced transfer
1/2 H2 + OH
Na+ Cl–
OH– H+ H+
process
Na+ Cl–
Cl– Na+
H+ OH–
1/2H2O
regeneration
H2O + e–
H2O
H2O H+
OH–
Process
Electro
H+
Concentrating Diluting Concentrating

Cathode compartment compartment compartment Anode
Concentrate Product Concentrate
FIGURE 24 Schematic presentation of electrodeionization (EDI) for ultrapure water production.

(Please refer to the online version for the color representation of the figure.)
Under the influence of the applied electric gradient, the ions present in the DC
exchange with mixed bed of IER and, simultaneously, get transferred to the CC through
IEMs (AEM and CEM). Thus, the DC gets depleted in ions, which accumulate in the
CC. The IER plays an important role in EDI process because of (i) faster ion transfer and
(ii) reduction in system resistance and back diffusion of ions from the CC to the DC. The
rate-determining step in this process is the diffusion of ions from the bulk solution to the
IER surface and the simultaneous production of H+ and OH− by water splitting which
regenerates the mixed bed of IER (87). Recently, EDI was employed to separate and
recover heavy metal ions (Ni2+ , Pb2+ , Zn2+ , Cr(VI), Co2+ , and Cu2+ ) from wastewater
solutions (88, 89). EDI has been considered as tool for ED with the ion-exchange
process. A mixed bed of IERs extract salt ions from water and act as channels
responsible for ion migration. Furthermore, water splitting is not enough to produce
sufficient H+ and OH− for resin regeneration because of the low transport efficiency
of H+ (tH+ = 0.00004–0.11) for CEMs and of OH− (tOH −
= 0.03–0.60) for AEMs. EDI
is coupled with EDBPM to enhance the water-splitting efficiency and generation of
H+ and OH− for resin regeneration. In this process, more number of H+ and OH− are
provided for resin regeneration due to high water splitting (tH+ and tOH −
= 0.90–0.96).
Continuous electrodeionization (CEDI) with a BPM, that is, CEDI-BPM, is used to
obtained ultrapure water (Fig. 25). It consists of CER and anion-exchange resin (AER)
beds in the DC while CEM and AEM to separate DC and CC, respectively. Under the
influence of the applied electrical gradient, water splitting occurs at the BPM interface,
resulting in simultaneous migration of H+ and OH− to the DCs. Reverse osmosis (RO)
treated water was fed into DC where mineral cations (Me+ ) were exchanged with H+ ,
and the exchanged Me+ migrated into the CC through the CEM (90).
Feed
1/4 O2 + H+ + e–
1/2 H2 + OH–
Me+ Me+
OH– H+
A–
A–
OH–
H2O + e–
H+
1/2H2O
H2O
H2O H+
–
OH
Cathode Anode
Repeating unit
CER AEM
AER CEM BPM
FIGURE 25 Schematic presentation of CEDI with bipolar membranes (CEDI-BPM) for pure
water production. (Please refer to the online version for the color representation of the figure.)
4.1.1.5 Bipolar Membrane Electrodialysis (EDBPM) for Production of Acid and Base
from Salt. In EDBPM, CEMs and AEMs are placed together with a BPM in an alternating
arrangement between electrodes to separate the electrode wash, feed, acid, and base
compartments, as depicted in Figure 26. Under the influence of the applied electric
gradient, charged species (A+ and X− ) get removed from the feed compartment (AX,
salt solution) through AEMs and CEMs. H+ and OH− produced at the BPM interface are
responsible for the migration of charged species from one compartment to the other. Thus,
the migrating charged species react with H+ and OH− which results in the formation
of acid (HX) and base (AOH) while the feed compartment become desalted. EDBPM
has been effectively used in industries to recover valuable chemicals from salts without
using any hazardous chemicals and additives.
EDBPM was carried out in two- and three-compartment cell configurations for the
conversion of salt into acid and base (Fig. 27a and b). The two-compartment cell config-
uration is simple and easy to use, in which base is transported from the cathodic to the
anodic compartment. Transport of the base is serious drawback and reduces the process
efficiency and product recovery; this can be avoided by using the three-compartment cell
configuration (91). EDBPM process has been used to convert NaCl into HCl and NaOH
by water splitting. The results showed that recovery and current efficiency (CE) were low,
but these parameters could be improved by modifying the EDBPM configuration: that is,
by changing the EDBPM cell into the three-compartment configuration. Thus modified
cell was also used to convert sodium salts (NH4 NO3 , NaNO3 , and Na3 PO4 ) into acids
and base (92). Recently, EDBPM with the three-compartment cell configuration was used
to convert NH4 NO3 into HNO3 and NH3 by water splitting, where ammonia was used
as the stripping solution (Fig. 27b) (93).
4.1.2 Electromembrane Processes for Biomolecular Separation and Recovery.
4.1.2.1 Separation and Recovery of Amino Acids from their Mixtures. AAs are being
extensively used as permitted chemicals, as additives in pharmaceutical products, in
Acid(HX)
Diluted salt (AX)
EW
EW
H+ OH– X– X– A+ A+
X– X– A+ A+
Anode
H+ OH
Cathode
EW
H2O
Salt (AX)
AEM CEM BPM
FIGURE 26 Schematic presentation of electrodialysis with bipolar membrane (EDBPM) for acid
and base production from their salts. (Please refer to the online version for the color representation
of the figure.)
Base: Depleted Acid:

Acid: HX Base: BOH BOH salt HX
(A) (B)
B+ B+
Water
B+ OH– H
H+ OH–
X– X–
+ – +
– H+ OH B+ B+X– X–
X– X– A+ A+
X–
EW
EW Water
Water Water
Salt: BX
AEM CEM BPM
FIGURE 27 (a) Two-compartment and (b) three-compartment EDBPM arrangement for con-
verting salts into acid (HX) and base (BOH). (Please refer to the online version for the color
representation of the figure.)
solid-phase peptide synthesis, as well as in agrochemical and biomedical sensor. Demand

of AAs is growing day by day worldwide, and they are being produced from molasses
and raw sugar by fermentation technology. AAs are amphoteric in nature and exist as
cations, anions, or zwitterions, depending on the solution pH (94). Separation of AAs from
fermentation broths depends on the following factors: (i) solubility, (ii) molecular size,
(iii) charge, and (iv) affinity. Generally, ion-exchange process has been used for separation
and purification of AAs from fermentation broths but, in this process, large quantities
of waste are created during IER regeneration. With growing international concern over
environmental issues, waste increases the treatment cost and deteriorates the effectiveness
of processes for the separation and recovery of AAs from their mixture. Therefore, there
is an urgent need to develop alternate IEM-based separation processes to separate and
recover AAs from fermentation broths. The ED/EMP has been used as an alternative
process for AA separation and recovery from fermentation broths.
Various reports are available in the literature for desalting AAs and separating them
from their mixture with salts by ED/EMP (94, 95). Shaposhnik et al. studied AA trans-
port through IEMs by ED, and their investigation showed that maximum ampholyte ions
flux was obtained at limiting current density, above which a decline in flux occurred.
This decline was due to (i) the barrier effect of the boundary layers, (ii) the decrease
in pH at the boundary layer of AEM, and (iii) the increase in pH at the boundary layer
of the CEM. Changes in pH recharge the ampholyte ions and further block their migra-
tion from one compartment to the other through IEMs under the influence of an applied
electrical gradient. The barrier effect may be alternate mechanism to effect AA separa-
tion and purification problems occurring in fermentation broths and biotechnology (95).
Furthermore, phenylalanine was also separated and recovered from fermentation broths
containing at least AA and inorganic salts (Na2 SO4 , (NH4 )2 SO4 ) (96). Electrotransport
of tyrosine was carried out using ED, and only diffusive transfer was observed. On the
basis of tyrosine transport, separation of tyrosine from binary mixtures (tyrosine/histidine

and tyrosine/arginine) was carried at various current densities, and results revealed that
the SF increased with the applied current density. Maximum separation was achieved
in case of tyrosine/histidine and tyrosine/arginine mixtures. Thus, ED can be efficiently
used for the separation of AAs from their binary mixtures present in a fermentation broth.
Aghajanyan et al. (97) developed an ED process to separate and recover proline from
proline model solution and fermentation broths containing chalk-free l-proline, l-valine,
and l-alanine. Desalting of the AA mixture solution was performed in five- and six-
compartment cells. The separation performance was better in the six-compartment cell
than in the five-compartment cell. Also, neutral AAs were also separated from biologically
active substances and salt solution mixtures (98).
Shahi et al. developed an EMP for AA separation from their mixtures by the isoelectric
focusing (IEF) technology. Glu and Lys separation from their mixture was carried out in
an EMP cell in which the feed chamber (FC) and permeate chambers (PC) were separated
by an AEM, while the electrode chambers (catholyte and anolyte) were separated by a
CEM. Separation of Glu and Lys (0.01 M) from their mixture was carried out in an
EMP cell at a constant applied potential (5.0 V) and pH 8.0. Results revealed that
initially the (SF) was low, but reached approximately 7.5 after passage of an appropriate
charge because AEM allowed Glu− transport, while Lys+ was retained in FC. The high
SF revealed the feasibility of EMP for separation of a Glu and Lys mixture at pH 8.0.
Furthermore, Glu and Lys transmission was strongly dependent on charge on transmitting
species, solution pH, the nature of charge on the membranes, and the applied electrical
gradient. Separation of Glu and Lys was achieved at a constant applied potential as a
result of the difference in their pI values, in spite of their very close molecular weights
and sizes. Thus, EMP may be an important tool for separation and recovery of AAs with
close molecular weights using IEF technology (94).
4.1.2.2 Electrodialysis Fermentation (EDF). Organic acids are produced from bacterial
fermentation of carbohydrates on the industrial scale and several processes have been
developed for the isolation and recovery of concentrated organic acids from fermentation
broths. Recently, EDF was used for this purpose because in this process the pH of the
fermentation broths was maintained during the separation of organic acids. EDF was used
to separate and recover lactic acid (Lah) from fermentation broth, in which the bacterium
Lactobacillus rhamnosus acted as the Lah producer (99).
4.1.2.3 Electrophoretic Membrane Contactor (EPMC) for Biomolecules Separation.

Separation and purification of biomolecules (proteins, polysaccharides, vitamins,
antibodies, and AAs) is an integral part of bioprocessing industries. Thus, there is
an urgent need to develop membrane technology to fractionate biomolecules because
their demand has been increasing in the food and pharmaceutical industries (99).
Conventional separation techniques such as affinity separation, chromatography, and
electrophoresis have been used in bioindustries for this purpose. Electrophoresis is
an electrodriven separation technique that has been utilized for the separation and
purification of biomolecules in downstream processes. But these processes are not
suitable for large-scale production because of the low product recovery and high
operational cost. Thus, highly selective and cost-effective membrane-based separation
processes for isolation and recovery of biomolecules are urgently required for academic
and industrial research (99). Ultrafiltration has been used to fractionate protein mixtures
Concentrate Dilute Concentrate Dilute

(A.B) (A.B) A (A.B)
B+
A– + – A– +
–
Electrode Electrode
Electrode Feed Electrode Elution Feed
buffer buffer
buffer (A– and B+) buffer –
chamber (A and B ) +
Seprating chamber Seprating chamber

AEM CEM Ultrafiltration membrane
(a) (b)
FIGURE 28 Schematic presentation of electrophoretic membrane contractor. (a) Separation

mode. (b) Elution mode. (Please refer to the online version for the color representation of the
figure.)
from fermentation broths (100). But major problem in this process is the decline in
protein flux after long runtime because of fouling and poor selectivity of membranes
towards specific proteins in the protein mixtures. EMP offers the option to enhance
purity and recovery of proteins from their mixture present in fermentation broths without
affecting separation efficiency. In the ED process, migration of bulky molecules (more
than ∼ 500 Da MW) is impossible due to the dense nature of the IEMs. Thus, use
of porous charged membranes in EMP (EPMC) may be a substitute for IEMs for the
separation and recovery of biomolecules (polyamino acids, peptides, proteins, and CS
oligomers) from their mixture (101). EPMC is a hybrid EMP in which an ultrafiltration
membrane (UFM) is used as the molecular barrier and the applied electrical gradient
is used as driving force for ion migration from one compartment to another. The
separation chamber is composed of two compartments (PC and FC) which are separated
by porous IEMs, and the electrodes are separated by dense IEMs (CEM and AEM)
to avoid denaturation of biomolecules. Under the influence of the applied electrical
gradient, charged molecules (A− and B+ ) migrate towards PC through porous UFMs,
and the solute mass flow depends on electrophoretic mobility of biomolecules. EPMC
is operated in two different modes, as depicted in Figure 28a and b.
This process was used to fractionate biomolecules from a complex feedstock solution
(102, 103). EPMC was used to separate α-lactalbumin (α-lg) from its mixture with bovine
hemoglobin. It was reported that the separation and production rate were enhanced up to
five times with feed concentration (104). β-Lactoglobulin (β-lg) is a major whey protein
that is released from the enzymatic hydrolysis of various bioactive peptides. However,
it is necessary to fractionate the protein hydrolysates to obtain more purified proteins.
Poulin et al. (105) used EPMC to separate and recover β-lg hydrolysate from a mixture.
EPMC was also used to fractionate peptides from a β-lg tryptic hydrolysate mixture and
separation of chitosan oligomers (106).
4.2 General Description and Application of Membrane Electrolysis

4.2.1 Production and Recovery of Organic Acids. There is growing interest in the
separation and recovery of organic acids because of their increasing demand in the
food and pharmaceutical industries. Organic acids are obtained as a mixture of their
salts and used as acidifying agents, preservatives in food industry, detergents, and raw
material for production of biodegradable polymers or biosolvents. Various purification
steps are necessary to obtain organic acids from fermentation broths, and approximately
50–80% products are obtained after 8–10 unit operation, which reduces the success of
the process for their separation and recovery. The level of impurities (sugars, polyols,
minerals, and coloring reagents) in organic acid mixtures depends on the manufacturing
process and chemical consumption in various separation processes such as precipitation,
crystallization, adsorption, or ion exchange. EED-based water-splitting technology was
employed to convert salts into acids from fermentation broths. EED was also used for
the separation and recovery of formic, acetic, butyric, valeric, adipic, caproic, and oxalic
acids from waste fermentation broth solutions, as well as for the production of malic
acid, partial electroneutralization of D-α-p-hydroxyphenylglycine (pHPG), conversion of
phenoxides into phenols, and Lah production from its sodium salts (LANa) (107–110).
Shahi et al. developed an EMR for in situ ion substitution and single-step separation
and recovery of Lah from its lactate salts. Experiments were carried at various applied
electrical gradients and various LANa concentrations in the CC and DW were fed into
anodic compartment. With progress of the experiment, lactate ions (LA− ) migrated from
the CC to the AC and, simultaneously, H+ was generated at the anode by water splitting.
Two steps were involved in this process: (i) migration of LA− from CC to AC across
AEM and (ii) LA− reacting with H+ leading to the formation of Lah in AC. A schematic
presentation for LA− migration and electrode reactions is depicted in Figure 29.
Single-step in situ ion substitution and separation of 1.0 M ammonium lactate
(LANH4 ) solution at 8.0 V/cm was also carried out in a proposed EMR as a represen-
tative case. Data revealed that the lactate flux was strongly dependent on the applied
electrical gradient and initial feed concentration of LA− in the CC. In this process,
NaOH LAH
AEM
1/4 O2 + H+ + e–
1/2 H2 + OH
OH– +H
Cathode
Anode
+
Na
LA–
H2O + e–
H2O
1/2H2O
H2O
LANa
FIGURE 29 Schematic presentation of the lactate ion (LA− ) transfer and Lah recovery. (Please
refer to the online version for the color representation of the figure.)
NaOH RH
CEM CEM
1/4 O2 + H+ + e–
1/2 H2 + OH
+H +H
OH–
Cathode
Anode
R–Na+
Na+
H2O + e–
1/2H2O
H2O
H2O
RNa
FIGURE 30 Schematic representation of EMR-3/EMP for the separation and recovery of car-
boxylic acids (RH) from their sodium salts (RNa). (Please refer to the online version for the color
LA− was transported into the AC and uncharged molecules such as polysaccharides,
carbohydrates, and other colouring agents were retained in the CC. Moreover, ion
substitution and separation of Lah in a single step could be achieved without use of any
additives or hazardous chemicals (110). EMP for in situ ion substitution and separation
of salicylic acid (SAH) from its sodium salt (SANa), was also developed by same
group. In situ ion substitution and separation of SAH from SANa was carried out in an
EMP cell. The electrochemical principle of EMP is illustrated in Figure 30.
Three steps were involved in this process: (i) formation of OH− and H+ at cathode
and anode by reductive and oxidative water splitting; (ii) electrotransport of H+ from
the AC to the CC across the CEM; (ii) in situ substitution of Na+ by H+ which led
to the formation of SAH; and (iii) electrotransport of the liberated Na+ from CC to the
CC, thus forming NaOH. In this process, ion substitution was achieved by the combined
effect of electrode polarization reactions and the simultaneous migration of H+ and Na+ .
The overall electrochemical reaction for in situ ion substitution and SAH separation from
SANa can be written as follows:
ONa OH
COOH COOH
+ H+ + OH– + NaOH
SANa SAH
The developed EMP was a more efficient process for in situ ion substitution and
separation for SAH from SANa than ED (7).
An EED principle based EMR was developed for in situ ion substitution and separation
of ascorbic acid (ASH) from its sodium salt (ASNa). Three step were involved in this
process: (i) H+ and OH− generation by oxidative and reductive water splitting; (ii)
electromigration of H+ from the AC to the CC across the CEM and in situ substitution
of Na+ by H+ , which lead to the formation of ASH; and (iii) electromigration of Na+
from CC to CC across CEM and subsequent formation of NaOH (Fig. 30). The overall
electrochemical reaction for in situ ion substitution and ASH separation from ASNa can
be written as follows:
O O
HO HO
O Acidification O
+Na–O OH OH
H2O NaOH HO
ASNa ASH
The developed EMP was more efficient than ED for in situ ion substitution and sepa-
ration for ASH from ASNa. Production of NaOH as a by-product in CC was a spinoff
of the developed EMR (111). Low water-soluble organic acids and their salts formed
solid particles or suspended droplets, leading to (i) membrane fouling, (ii) pump erosion,
(iii) low product recovery, and (iv) unstable operation. These problems could be solved
by using specific organic solvents that induce organic acid solubility. Selection of the
organic solvent plays an important role in two-phase electro-electrodialysis (TPEED) and
the modified two-phases electro-electrodialysis (MTPEED) processes. TPEED is a com-
bination of two-phase electrophoresis (TPE) and EED. In this process, the two phases are
separated by an AEM, and pure organic solvent or a water–organic (W/O) emulsion is
used as the extracting medium. Electroosmosis, osmosis of water, and backdiffusion are
well controlled in TPEED. Thus, low water-soluble organic acids can be easily concen-
trated and recovered from very dilute waste fermentation solutions (112). This process
has been used to concentrate and recover organic acids from model and fermentation
broth solutions (12, 113–115).
EDBPM processes have been utilized for the production of organic acids such as Lah,
pHPG, propanoic acid, tartaric acid (H2 Tar), pyruvic acid, gluconic acid, formic acid,
acetic acid, 2,2-dimethyl-3-hydroxypropionic acid, sebacic acid, and galacturonic acid
(GAH) (115, 116). Xu et al. studied the effect of cell configuration on EDBPM process
performance for the electro-acidification of H3 A. Three basic cell configurations, namely,
AEM–CEM–BPM–AEM–CEM, CEM–BPM–CEM, and BPM–AEM–CEM–BPM,
were used for H3 A production from its sodium salt (Na3 A). The energy consumed in the
CEM–BPM–CEM configuration was low and followed the trend, CEM–BPM–CEM <
AEM–CEM–BPM–AEM–CEM < BPM–AEM–CEM–BPM. It was reported that the
CEM–BPM–CEM cell configuration was more appropriate for H3 A production (117).
4.2.2 Production of Tetrabutyl Ammonium Hydroxide (TBAOH). Shahi et al. devel-

oped EMRs with two compartments (EMR-2) and three compartments (EMR-3) for the
efficient synthesis of tetrabutyl ammonium hydroxide (TBAOH) from tetrabutyl ammo-
nium bromide (TBABr) by in situ ion substitution and separation. Experiments were
carried out in EMR-2 at different applied current densities and TBABr concentrations.
TBABr of various concentrations was fed into the cathodic compartment, while DW was
fed into anodic compartment. In this process, the applied current density was mainly
responsible for OH− and H+ formation and migration of Br− , which resulted in the
variation of pH in both compartments. The complete electrochemical process for TBABr

conversion into TBAOH can be written as follows:
(C4 H9 )4 N+ Br− + OH− → (C4 H9 )4 N+ OH− + Br−
To evaluate the technical and economic feasibility of TBAOH synthesis in EMR-2,

W , CE (%), and recovery (%) of TBAOH were evaluated. The data revealed that W
increased, while CE and TBAOH recovery decreased with increase in applied current
density, for 0.10 M TBABr feed solution. More OH− was formed at high applied current
density. TBAOH formation may be high but this was not the case for more TBAOH
production. Reduction in CE may be due to (i) partial TBAOH degradation (Hofmann
elimination) and (ii) OH− leakage along with Br− from the cathodic to the anodic
compartment. To improve product recovery and CE, the EMR was modified in such a
way that TBABr was not in direct contact with the electrodes. Single-step, in situ ion
substitution and TBAOH synthesis from TBABr were achieved in EMR-3, as shown in
Figure 31.
Three steps were involved in this process: (i) OH− generation by reductive water
splitting and their migration from the cathodic compartment to the CC across the AEM;
(ii) substitution of Br− by OH− ; and (iii) migration of Br− from the CC to the anodic
compartment across AEM, forming HBr/Br2 . TBAOH synthesis rates in EMR-2 and
EMR-3 were compared under similar experimental conditions as a function of applied
current density and initial TBABr concentration in CC. The results revealed that TBAOH
flux was two times higher in EMR-3 than in EMR-2. TBAOH synthesis rate in EMR-3
increased with applied current density, while it reduced in EMR-2. Reduction in TBAOH
synthesis rate might be due to the high extent of degradation of TBAOH in EMR-2 as
compared to EMR-3. The developed EMR-3 may be used for efficient TBAOH synthesis
without the use of hazardous chemicals (9).
H2O TBAOH HBr
AEM AEM
1/4 O2 + H+ + e–
1/2 H2 + OH
OH– +
H
OH–
Cathode
Anode
Br– Br–
TBA+
H2O + e–
1/2H2O
H2O
TBABr
FIGURE 31 Schematic presentation of an electromembrane reactor for the synthesis of tetra-

butyl ammonium hydroxide (TBAOH) from the corresponding bromide by in situ ion substitution.
4.2.3 Chlor-Alkali Electrolysis. Electrolysis is used for synthesis of chemicals, in

which oxidation and reduction reactions occur at the respective electrodes. In this process,
anolyte and catholyte are separated by an IEM to prevent the mixing of the electrolyte
solutions. Chemicals can be produced by electrolysis because there is no need to use
catalysts or other additives (118). This process is based on NaCl electrolysis and on
the migration of ions from one compartment to another across the IEM. The following
reaction occurs in NaCl electrolysis by the chlor-alkali process.
2NaCl + 2H2 O → 2NaOH + Cl2 + H2
In this process, two major challenges exist: (i) Cl2 reacts explosively with H2 and
(ii) Cl2 dissolves in NaOH and forms a hypochlorite solution. Therefore, it is imperative to
separate and recover the reaction products. In an electrolysis cell, the anodic and cathodic
compartments are separated by a CEM (Fig. 32), while a saturated solution of NaCl is
fed into acidic compartment and DW to the cathodic compartment. Under the applied
electrical gradient, Cl2 gas is produced in the anodic compartment due to Cl− oxidation,
and, simultaneously, migration of Na+ takes place from the cathodic compartment across
the CEM and NaOH is formed. The concentration and pH of saturated brine solution
should be in the range 300–305 g/l and 2.0–4.0, respectively, (119) because athigh pH,
Cl2 reacts with OH− and forms hypochloric acid (HClO) or chlorate ions, as per reactions
below (120):
Cl2 + OH− → HClO + Cl−

HClO + H2 O + 2e− → 3H+ + Cl− + O2
HClO + ClO− → ClO− +
3 + 2H + Cl
−
The membrane used in chlor-alkali electrolysis should (i) have good physical and
chemical stability in alkaline and Cl2 media, (ii) have low membrane resistance,
(iii) only allow Na+ transport from anolyte to catholyte and Cl− transport from catholyte
NaOH
23–32% Depleted NaCl brine
Hydrogen H2
Chlorine Cl2
CEM
OH– Cl2
Cathode
Anode
H2O Cl–
Na+ Na+
NaCl brine
FIGURE 32 Schematic presentation of the chlor-alkali process for NaOH and Cl2 synthesis.
to anolyte, (iv) operate at high current densities, and (vi) be impervious to interfering
heavy metal ion impurities present in brine solution (120). CEMs (Du Pont, and Asahi
Glass Company) have been used for NaCl electrolysis to synthesize NaOH and Cl2 .
Removal of metal ions is necessary because they influence the product purity and
electrolysis efficiency. Salt splitting have been carried out using the chloro-alkali process
by many researchers to convert salts into acids and bases (121). Yazicigil et al. used the
chlor-alkali process to convert metallic salts into acids and bases. Potassium salts were
fed into the cathodic compartment and acid solutions were fed into anodic compartment,
both separated by an AEM. Furthermore, in another set of experiments, CEM was used
as the separator and base solutions were fed into cathodic compartment. Results revealed
that different salts of potassium were converted into acids and bases by water splitting and
migration of ions (anions or cations) across the IEM (AEM or CEM, respectively) (121).
4.2.4 Bipolar Membrane Electroacidification (BPMEA). BPMEA is a process based

on water splitting and further acidification for the fractionation of soy proteins, casein
production, and chitosan oligomer production, as well as the fractionation of whey pro-
teins. The effect of CEMs (CSV and CMX) permselectivity on cation skim milk protein
migration and precipitation was studied by BPMEA (122–126). It was reported that
highly pure bovine milk casein (97–98%) could be isolated and used for commercial
applications (127). BPMEA was also used to separate the α-lg fraction (98%) from the
whey protein isolate (WPI) solution (5%) (128). Electroacidification of WPI solution
(20%) at p, 4.65 was studied to investigate the effect of solution conductivity on protein
precipitation (129). Cheddar cheese whey protein was acidified by BPMEA, in which
whey lipids (30%) precipitated at pH 3.7 (130).
4.3 General Description and Application of Diffusion Dialysis

DD is an IEM separation process driven by concentration gradient and has been applied
for the separation and recovery of acid/alkali waste solutions in a cost-effective and envi-
ronmentally friendly manner. DD has been successfully applied for the recovery of acids
and alkalis from the discharges from steel production, metal refining, electroplating, CER
regeneration, nonferrous metal smelting, aluminum etching, and tungsten ore smelting.
The separation of HCl and NaOH from their feed solution is illustrated in Figure 33 to
describe the principle of DD. As shown in Figure 33a, HCl and its metal salts in the feed
solution tend to transport to the water side due to the concentration difference across the
membrane. Because of the presence of the AEM, the Cl− ions (SO4 2− , NO− 3−
3 , PO4 , etc.)
are permitted passage, while the metals in the waste solution are much less likely to pass.
The H+ ions, although positively charged, show higher diffusion than metal ions
because of their smaller size, lower valence state, and higher mobility. Hence they can
diffuse along with the Cl− ions (or SO4 2− , NO− 3−
3 , PO4 , etc.) to meet the requirement of
+
electrical neutrality. The H transport is a key to the DD process (131–133). Suitable
properties of the AEM are also necessary, including stability in acidic solution, high H+
permeability, strong rejection of other metal ions, relatively high water uptake (WR),
and poor water permeability. The separation process of NaOH from its feed solution
(Na2 WO4 as an example) is illustrated in Figure 33b. NaOH and Na2 WO4 tend to
transport to the water side due to the concentration difference across the membrane.
Because of the presence of the CEM, the Na+ ions in the feed are permitted passage,
while the WO4 2− ions are much less likely to pass through the membrane. Similar to
(a) (b)
AEM CEM
Water Side Feed Side Water Side Feed Side
Cl– Cl–
Na− Na−
M+
Cl– Cl–
Na– Na−
H− H−
OH− OH−
FIGURE 33 Schematic diagram illustrating the principle of diffusion dialysis. (a) HCl separation
process from its feed solution. (b) NaOH separation process from Na2 WO3 solution. (Please refer
to the online version for the color representation of the figure.)
H+ through an AEM, the hydroxyl ions (OH− ) diffuse better than the WO4 2− ions and,
along with Na+ ions, meet the requirement of electrical neutrality. The OH− transport
is also a key to the process (134), and CEMs with high stability in alkali solutions,
high OH− permeability, strong rejection for other anions, and relatively high WR, but
poor water permeability, are also required. Two methods have been generally used for
the DD process: the first one is a batch process, and the second one is a continuous or
pilot process. The batch process is schematically presented in Figure 34a, in which two
equal volumes are separated by an IEM, and one side is filled with the feed solution and
the other side with fresh water. For decreasing concentration polarization, both solutions
are stirred by mechanical stirrers continuously. This process is generally used in the
laboratory for the calculation of diffusivity andSF.
Continuous dialysis is based on the batch process but uses a number of IEMs in
a dialyser for the recovery of acid or base (Fig. 34b). For decreasing concentration
polarization, both the feed solution and water are moved by a pump. The data obtained in a
continuous dialysis can be more valuable for practical reference because the experimental
conditions are more similar to those in a practical dialysis unit.
4.3.1 Inorganic Acid Recovery. A number of inorganic acids are used in the industrial
processes such as steel production and metal refining, nonferrous metal smelting, etc. For
the recycling of acid from the metal salts, different methods are used, such as cooling
and crystallization, thermal decomposition, evaporation and crystallization, ion exchange,
solvent extraction, distillation, and electromembrane separation, as well as direct disposal
and neutralization with alkalis. But all these methods consume considerable amounts of
energy, and so new, sustainable methods such as DD, are required. Many workers have
recovered H2 SO4 , HNO3 , HCl, and HF from different solutions using IEMs (Table 3).
4.3.2 Organic Acid Recovery. Organic acids have been widely used in chemical,
leather, food, fermentation, and pharmaceutical industries. Among them, industries
using bacterial fermentation always generate carboxylic acids and carboxylates of
various compositions and concentrations (159). Acids are toxic to bacteria during the
(a) Stirrer Stirrer
M
AE
Cl– Cl–
Feed Solution
Water Solution
M+
Cl– Cl– M+
H−
H−
(b)
Recovered acid
Depleted
Solution AEM AEM AEM
Cl– Cl– Cl– Cl– Cl– Cl–
M– M+
Cl– Cl–
Cl– Cl– Cl– Cl–
H− H− H− H− H− H−
Feed
water Feed
solution
FIGURE 34 Experimental set up for diffusion dialysis. (a) Batch process. (b) Continuousbreak
dialysis. (Please refer to the online version for the color representation of the figure.)
fermentation process, and the pH of the broth should be in the range of 5–6 (160,
165). Hence different methods (163, 165), including facilitated membrane extraction,
neutralization dialysis, IERs, as well as integrated systems of ultrafiltration and ED
have been used to remove acids from the broth. Meanwhile, DD, as a simpler and
more economical method, has been studied for the recovery of weak acids from those
industries. Some work in the recovery of some carboxylic acids is systematized in
Table 3.
4.3.3 Base Recovery. Alkali waste is mainly generated from paper, leather, printing
and dying, tungsten ore smelting, and manmade fiber industries (166–169). DD is the
lowest cost-effective process for the recovery of alkali from such waste. Around 20
years ago, Astom Corporation of Japan developed an alkali-resistant CEM, which was
responsible for the remarkable progress in DD (166). Furthermore, Astom Corporation
also successfully developed a DD process to recover NaOH from an aluminum etching
TABLE 3 Application Diffusion Dialysis in Inorganic and Organic Acid Separation
Recovered Research and Scale Membrane Process Characteristic References
Acid Application Field
H2 SO4 Separation of Laboratory scale (batch Neosepta-AFN (Astom Membrane area 62.2 cm2 ; temperature 135
H2 SO4 + CuSO4 dialysis) Corporation, Japan) 20 ± 0.5 ◦ C; R CuSO4 > 0.965 in case
mixture of C CuSO4 > 0.75 kmol/m3
H2 SO4 recovery from Pilot scale: Asahi Type Selemion DSV (Asahi Membrane area 0.327 m2 ; membranes 136
waste acid solution T-0b Dialyzer Glass, Tokyo, Japan) number 19; R H2 SO4 80–57%; R NiSO4
and R FeSO4 96 and 99%;
S
H2 SO4 /FeSO4 15–18, S H2 SO4 /NiSO4
140–270
H2 SO4 and Ni Laboratory scale and Pilot Brominated PPO-based Membrane effective area 2.32 m2 ; 137
R
recovery from runs (industrial scale) AEM (Shandong, NiSO4 > 96%; R H2 SO4 66–72%
electrolysis spent China)
solution
H2 SO4 recovery from Pilot scale: Asahidialyzer Selemion DSV (Asahi Membrane area 0.326 m2 ; membranes 138
waste aluminum (Model T-O) Glass, Tokyo, Japan) number 19; R H2 SO4 82–90%;
surface processing R Al (SO ) 35.3–38.5%
2 4 3
solution
Separation of Laboratory scale (batch Neosepta-AFN (Astom Membrane area 62.2 cm2 ; transport of 139
H2 SO4 + ZnSO4 dialysis) Corporation, Japan) negatively charged complexes of Zn2+
mixture being controlling step
H2 SO4 recovery from Pilot scale: TSD-2 DF 120-I (Shandong, Membrane area 0.02 m2 ; membranes 140, 141
rare earth sulfate dialysis cell China) number 11; one-pass and cycling
solution (Tokuyama Ltd. Japan) operation; R H2 SO4 70–80%
H2 SO4 recovery from Pilot scale DF 120-I (Shandong, Membrane area 1.9 m2 ; S H2 SO4 /FeSO4 142
titanium white acid China) 23.6; mR H2 SO4 > 85%; R FeSO4 > 93%
by DD
H2 SO4 recovery from Pilot scale DF 120-I (Shandong, Membranes number 40; RH2 SO4 80%; 143
hydrometallurgy China) RV 96%
leaching solution
45
(continued overleaf)
TABLE 3 (Continued)
46
H2 SO4 recovery from Laboratory scale Brominated PPO-based Membrane area 5.07 cm2 ; S H2 SO4 /Ti 51 144, 145
titanium white AEM (Shandong,
(pigment) waste China)
solution
Waste acid recovery Industrial scale DF 120-I (Shandong, R H SO
2 4 about 80%; C H+ (recovered) 146
from Hua Cheng China) 4.4–5.2 g/l
Foil Factory
Acid recovery by DD Pilot scale DF120-I (Shandong, Membrane area 4 m2 ; R H2 SO4 and 147
R
in chemical fiber China) Na2 SO4 70–80%; R COD about 70%
factory
H2 SO4 recovery from Laboratory scale (cycling — Membrane area 54 cm2 ; R H2 SO4 30%; 148
R
solution containing operation) U <10%
uranium
H2 SO4 recovery from Pilot scale (HKY-001 DF120-III (Shandong, Membrane area 3.2 m2 ; R H2 SO4 80%; R V 149
acid leach solution dialyzer) China) 93–95%; R Fe 92–94%
H2 SO4 recovery from Laboratory scale; Pilot DF120-I (Shandong in Membrane area for lab scale 2.83 cm2 ; 150
waste anodic scale; China) Membrane area for pilot scale 3.2 m2 ;
aluminium H2 SO4 recovery 85.25%; Al3+ leakage
oxidation solution 4.98%
HCl HCl recovery Laboratory scale and pilot Neosepta-AFN Membrane area 16 cm2 for lab scale; 151
scale (TSD-2 dialyzer) (Tokuyama Co., Japan) membrane area 200 cm2 for pilot scale;
R
HCl 60–80%
HCl recovery from Laboratory scale Neosepta-AFN Membrane area 62.2 cm2 ; permeability for 152
solution containing (Tokuyama Co., Japan) HCl 0.84 × 10−6 to 2.4 × 10−6 m/s;
NiCl2 permeability for NiCl2 : two orders of
magnitude lower than that for HCl
HCl recovery from Laboratory scale Neosepta-AFN Tokuyama The partial flux of FeCl2 < 5.6%; the 153
solution containing Co., Japan) concentration gradient of FeCl2 has
HCl + FeCl2 significant effect on the salt flux
R
HCl recovery from the Pilot scale DF120-I (Shandong, HCl >88%; R Fe 89–77%; R Zn >56% 154
waste acid solution China)
HCl permeability Pilot scale Neosepta-AFN Tokuyama The permeability of HCl apparently 155
through Co., Japan) increases with acid concentration
Neosepta-AFN
HNO3 HF +HNO3 recovery Industrial scale Brominated PPO-based Membrane area 512 m2 ; R H+ 85% 156
from titanium spent AEM (Shandong,
leaching solutions China)
Tin and HNO3 Laboratory scale DF 120-I (Shandong, Membrane area 95 cm2 ; R HNO3 > 70% 157
recovery from the China)
spent solder stripper
CH3 COOH Transport of acetic Laboratory scale Neosepta AMH (Astom Membrane area 100 cm2 ; temperature 158
acid Corporation, Japan) 50 ◦ C; acid flux is proportional to acid
concentration, membrane permeability
is independent of acid concentration
C3 H6 O3 Separation of lactic Laboratory scale Neosepta AMH (Astom Membrane area 50 cm2 ; fluxes: 1 mol/m2 159
acid/lactates from Corporation); Selemion h for acid, 0.07 mol/m2 h for salt
fermentation DSV (Japan) separation factor: 20 for Neosepta
products AFN, 30 for DSV membrane
RCOOH Separation of Pilot scale Neosepta AFN (Astom Separation factor: 20–37 for AFN, about 160
carboxylic acids Corporation); Selemion 29 for Selemion DSV; Fluxes 1.5–2.0
from carboxylates DSV (Japan) for acid, 0.07–0.08 for salt
(continued overleaf)
47
48
TABLE 3 (Continued)
Transport of some Laboratory scale (batch Neosepta AMH (Astom Membrane area 62.2 cm2 ; the 161
carboxylic acids dialysis) Corporation, Japan) mass-transfer data of oxalic acid is the
largest (1.0 × 10−6 to 1.0 × 10−7 m/s,
nearly one order of magnitude higher
than others)
Continuous dialysis of Pilot scale Neosepta AMH (Astom Membrane area 3.31 × 10−2 m2 ; P values 162
carboxylic acids Corporation, Japan) of AMH 7.50 × 10−9 to 3.57 × 10−7
m/s, and its order:
PCA < PLA < PTA < PAA < POA
Solubility and Pilot scale Neosepta AMH (Astom The partition coefficients (acid 163
diffusivity of Corporation, Japan) concentration in membrane to that in
carboxylic acids in external solution) decrease with
membrane increasing acid in feed; The orders of D
values: DTA < DLA < DAA < DOA
HCOOH Transport of formic Laboratory scale (batch SB-6407 (Gelman Membrane area 7.07 cm2 ; AFN 164
acid dialysis) Sciences); Neosepta membraneshows the highest
AMH, AFN, ACM mass-transfer coefficient
(Japan)
solution. The production technique was industrialized in a California Caspian plant,

USA, around 1991 incorporating a diffusion dialyzer (TSD10-300 and TSD25-250) (166).
Inspired by initial successes of DD, recovery of alkali from an alkali etching solution
from the white tungsten ore smelting industry has been tried with dialyzer TSD-2-20 in
Japan (170). The feed alkali solution contains WO3 91.25 g/l and NaOH 1.36 mol/l. When
the flow rate of the feed and the recovered solution are controlled at 40 and 10 mol/min,
respectively, in a cyclic manner, the concentration of the recovered solution was up by
51% of feed concentration, and the recovery rate was 50% (136).
4.4 General Description and Application of Donnan Dialysis

Donnan dialysis is used to exchange ions between two solutions. The basic principle
of Donnan dialysis is schematically presented in Figure 35, which shows a two equal
volumes separated by a CEM, with the feed CuSO4 solution on one side and 1 N H2 SO4
on the other. The solution pH on the CuSO4 side is significantly higher than that of
the H2 SO4 side. The pH difference drives the H+ ions across the membrane, which
increases the H+ concentration in the CuSO4 side. Cation selection membranes only
pass the cations and repel the anions (SO4 2− ), which causes a potential difference, and
for maintaining equilibrium Cu2+ ions move to solution 2. A similar process is followed
by the AEM.
4.4.1 Separation of Salt from the Acid. With the help Donnan dialysis, an acid is easily
separated by its salt solution. Figure 36 shows how an intelligent use of the Donnan
membrane principle in an anion exchange column allows separation and recovery of
relatively pure citric acid from a fermentation broth in the presence of citrate salts (171).
CEM
Solution 1 Solution 2
CUSO4, PH = 7 H4SO4, PH = 1
H− H−
SO4–2
SO4–2
Cu2− Cu2−
FIGURE 35 Schematic diagram illustrating the principle of Donnan dialysis using a CEM and
a pH gradient to exchange copper ions against hydrogen ions. (Please refer to the online version
for the color representation of the figure.)
CEM
Solution 1 Solution 2
RCOONa HCl
H− H−
RCOO
Cl–
Na− Na−
FIGURE 36 Recovery of organic acid from their salt solution. (Please refer to the online version
for the color representation of the figure.)
Owing to the Donnan membrane effect, the salt co-ions (e.g., Na+ , Mg2+ , Ca2+ ) are
well excluded from the inside of the AERs containing nondiffusible quaternary ammo-
nium (R4 N+ ) groups.
4.4.2 Coagulant Recovery. According to Second Law of thermodynamics, a solute

always moves from a higher concentration to a lower concentration, but in Donnan
membrane process it is possible, although counterintuitive, to drive ions from a lower
to a higher concentration region and concentrate (such ions) even in the absence of
electricity (external work). Worldwide, there are approximately 10,000 drinking water
treatment plants where commercial alum is used for coagulation of suspended particles.
In the coagulation process, aluminum sulfate is converted to undissolved Al(OH)3 and
disposed of in land. But in Donnan membrane process, alum is recovered and further
utilized. In Figure 37, the Donnan membrane process for the recovery of alum from
waste Al(OH)3 is shown.
4.5 General Description and Application of Reverse Electrodialysis (RED)

The production of energy by mixing sea and river water through IEMs is referred to as
RED (Fig. 38). The RED process provides clean and sustainable energy, and is based on
the concentration gradient. The design of a stack to be used in RED is very similar to
that used in ED. The main difference is that the cells are arranged in parallel between
the electrodes and are rinsed alternately by sea and by river water. The ions in the sea
water (Na+ and Cl− ) permeate into the river water through the corresponding IEM and
produce brackish water due to their electrochemical potential gradient. This leads to an
electrical current between the cathode and the anode.
Water treatment residuals (WTR) Dilute sulfuric acid

Impermeable
Natural organic
matter, anions,
neutral
molecules Permeable
AI3+
Permeable
3H+ 3H+
AI3+
Impermeable
AI(OH)3(s) Impermeable
CI– SO42–
FIGURE 37 Single-step Donnan membrane process illustrating selective coagulant recovery

from water treatment residuals (WTRs). Source: Reprinted with permission from Reference 171.
Copyright (2010) American Chemical Society. (Please refer to the online version for the color
River water
Condensation Water Flow

Evaporation
Anode
Cathode
Sea water
Na− Anion-exchange membrane
Cl− Cation-exchange membrane
FIGURE 38 Schematic representation of the natural water cycle and energy production by using
reverse electrodialysis. (Please refer to the online version for the color representation of the figure.)
The maximum energy recovered in the RED process is equal to Gibbs free energy of
mixing (mix G) of fresh water to sea water, which is given by:
mix G = Gb − (Gc − Gd ) (21)

mix G = −(nc + nd )T mix Sb − (nc T mix sc − nd T mix sd ) (22)
where the subscript c stands for the concentrated salt solution (e.g., sea water), the
subscript d is for the dilute salt solution (e.g., river water), and the subscript b is for the
resulting brackish salt solution. n is the amount (moles), and T is the temperature; mix s
represents the contribution of the molar entropy of mixing (J/mol · K) to the total molar
entropy of the corresponding electrolyte solution, according to

mix s = −R xi ln xi (23)
i
where R is the universal gas constant (8.314 J/mol · K), and x is the mole fraction of
component i (i = Na, Cl, H2 O). The theoretically available amount of energy from mixing
1 m3 of fresh water with 1 m3 of sea water having a total salt content of ca. 35 kg/m3
is ca. 0.4 kWh. Unfortunately, the actual recovered energy is lower than the theoretical
value and it can calculated by the open voltage multiplied by current carried by ion
diffusion of sea water in to river water and stack resistance.
For a completely semipermeable IEM, the open voltage is calculated by the following
equation:
RT a
Usto = ln c (24)
F ad
where Usto is the open voltage of a stack, R is the gas constant, T is the absolute tem-
perature, and ac and ad are the equivalent activities of the concentrated and diluted cell,
respectively.
The maximum power that can be generated is given as
(U o )2
Wmax = IUsto = I 2 Rst = (25)
Rst
where Wmax is the maximum power output, I is the current of the stack, and R is the
resistance of stack. Stack resistance is the most important parameter for increasing the
maximum power density; it can be reduced by making the layers as thin as possible
to decrease the concentration polarization area. From the literature, it is found that the
maximum power density that is achieved to date in practical application is 0.5–1.0 W/m2
(107). Therefore, it seems that the membrane costs must be drastically decreased to make
RED a competitive energy production process. But better and thinner membranes and
cells, as well as low cost of membranes, which most likely will be developed, will
increase the competitiveness of RED in the future.
5 CONCLUSIONS AND FUTURE PERSPECTIVE
ED, which is based on IEMs, has been well proven for water desalination and purifica-
tion. However, new applications of ED and other related processes are rapidly developing
for separation, downstream process, and water-splitting technology. New challenges in
water and wastewater treatment, chemical processing, and food and biotechnology indus-
try will also accelerate the requirement of ED and related processes. For these processes,
highly selective, conductive, stable, and durable IEMs are urgently required. Develop-
ment of specific membrane-forming materials has been receiving interdisciplinary efforts
since last two decades. Several types of functionalized polymers and organic–inorganic
FIGURE 39 Research status and application of electromembrane processes. (Please refer to the online version for the color representation of the figure.)
53
nanocomposite materials are most appropriate to produce highly stable and permselective
IEMs. Intensified researches on IEM-based EMPs have been accomplished during recent
years to produce potable water, separation and recovery of toxic components, and down-
stream processing for biomolecular separation and recovery. The choice of the proper
membrane, design, and operational optimization of the process are highly essential for
successful commercialization of any process (Fig. 39).
Thus, the development of cost-effective membranes by the eco-friendly route is highly
urgent for researchers working in the membrane-based electrochemical separation pro-
cess filed. Current IEM research starts with requirement of membrane properties for
a specific process, elucidation of membrane structure, and design of the membranes
from molecular-level tailoring. The relationship between separation results and mem-
brane function should be studied properly for successful membrane developments. In
addition, the relationship between the membrane microstructure and operation parame-
ters of EMP has also a valuable impact. Some of IEM applications should be considered
as state of the art for technology development, such as water desalination/purification
and EDI, and BPMs for the production of organic acids from their salts present in
fermentation.
Often, EMP competes with other mass separation techniques from economic consid-
erations, but in some applications EMPs provide higher quality products and are more
environmentally friendly. These processes can be used as alternatives for the separation
and recovery in spite of their cost disadvantage. An interdisciplinary approach should help
develop EMP for water treatment, biomolecular separation, waste treatment, and energy
production, as well as integrate recent advances and knowledge on material, inorganic,
polymer science and technology, mathematics, and engineering to solve some multifold
problems and design of apparatus for EMPs.
ACKNOWLEDGMENT
The authors wish to acknowledge the services of the Analytical Sciences Division,
CSMCRI, Bhavnagar, India, for instrumental support. One of the authors (AKS) is grate-
ful to the Council of Scientific and Industrial Research (CSIR), New Delhi, India, for
providing a Senior Research Fellowship (Ext).
REFERENCES
1. Nagarale RK, Gohil GS, Shahi VK. Adv Colloid Interface Sci 2006;119:97–130.
2. Fidaleo M, Moresi M. J Membr Sci 2011;367:220–232.
3. Saakes DAVM, Nijmeijer K. J Membr Sci 2011;385–386:234–242.
4. Service RF. Science 2002;296:1222–1224.
5. Greiter M, Novalin S, Wendland M, Kulbe KD, Fischer J. J Membr Sci 2002;210:91–102.
6. Khan J, Tripathi BP, Saxena A, Shahi VK. Electrochim Acta 2007;52:6719–6727.
7. Liberatore R, Ceroli A, Lanchi M. Int J Hydrogen Energy 2008;33:4283–4290.
8. Kumar M, Tripathi BP, Shahi VK. Electrochim Acta 2009;54:4880–4887.
9. Kumar M, Tripathi BP, Shahi VK. Ind Eng Chem Res 2009;48:923–930.
10. Himmler S, Konig A, Wasserscheid P. Green Chem 2007;9:935–942.
11. Kumar M, Tripathi BP, Saxena A, Shahi VK. Electrochim Acta 2009;54:1630–1637.
12. Lu YC, Yi SS, Luo GS. J Membr Sci 2008;322:265–274.
13. Bolto B, Hoang M, Tran T. Desalination 2010;254:1–5.
14. Huang CH, Xu T. Environ Sci Technol 2006;40:5233–5243.
15. Shapiro V, Freger V, Linder C, Oren Y. J Phys Chem B 2008;112:9389–9399.
16. Nagarale RK, Shahi VK, Thampy SK, Rangarajan R. React Funct Polym 2004;61:131–138.
17. Hosseini SM, Madaeni SS, Khodabakhshi AR. J Membr Sci 2010;351:178–188.
18. Shahi VK, Thampy SK, Rangarajan R. React Funct Polym 2000;46:39–47.
19. Nagarale RK, Gohil GS, Shahi VK, Rangarajan R. Colloids Surf A, Physicochem Eng Aspects
2004;251:133–140.
20. Choi E-Y, Bae B, Moon S-H. J Phys Chem 2007;B111:6383–6390.
21. Varcoe JR, Slade RCT, Yee ELH, Poynton SD, Driscoll DJ, Apperley DC. Chem Mater
2007;19:2686–2693.
22. Sachdeva S, Kumar A. J Membr Sci 2008;307:37–52.
23. Savari S, Sachdeva S, Kumar A. J Membr Sci 2008;310:246–261.
24. Qiu Z, Wu S, Li Z, Zhang S, Xing W, Liu C. Macromolecules 2006;39:6425–6432.
25. Yin Y, Fang J, Watari T, Tanaka K, Kita H, Okamoto K. J Mater Chem 2004;14:1062–1070.
26. Guo X, Zhai F, Fang J, Laguna MF, Lopez-Gonzalez M, Riande E. J Phys Chem B
2007;111:13694–13702.
27. Nagarale RK, Gohil GS, Shahi VK. J Membr Sci 2006;280:389–396.
28. Wang J, Zhao Z, Gong F, Li S, Zhang S. Macromolecules 2009;42:8711–8717.
29. Hibbs MR, Hickner MA, Alam TM, McIntyre SK, Fujimoto CH, Cornelius CJ. Chem Mater
2008;20:2566–2573.
30. Wu L, Xuand T, Yang W. J Membr Sci 2006;286:185–192.
31. Xu T, Liu Z, Li Y, Yang W. J Membr Sci 2008;320:232–239.
32. Choi Y-J, Park J-M, Yeon K-H, Moon S-H. J Membr Sci 2005;250:295–304.
33. Tripathi BP, Saxena A, Shahi VK. J Membr Sci 2008;318:288–297.
34. Kang M-S, Cho S-H, Kim S-H, Choi Y-J, Moon S-H. J Membr Sci 2003;222:149–161.
35. Kumar M, Singh S, Shahi VK. J Phys Chem B 2010;114:198–206.
36. Kickelbick G. Prog Polym Sci 2003;28:83–114.
37. Nagarale RK, Gohil GS, Shahi VK, Rangarajan R. Macromolecules 2004;37:10023–10030.
38. Zuo X, Yu S, Xu X, Bao R, Xu J, Qu W. J Membr Sci 2009;328:23–30.
39. Klaysom C, Marschall R, Wang L, Ladewig BP, Lu GQM. J Mater Chem 2010;20:
4669–4674.
40. Kumar M, Tripathi BP, Shahi VK. J Membr Sci 2009;340:52–61.
41. Nagarale RK, Gohil GS, Shahi VK, Rangarajan R. J Colloid Interface Sci 2005;287:198–206.
42. Zuo X, Yu S, Xu X, Xu J, Bao R, Yan X. J Membr Sci 2009;340:206–213.
43. Singh S, Jasti AN, Kumarand M, Shahi VK. Polym Chem 2010;1:1302–1312.
44. Balster J, Stamatialis DF, Wessling M. Chem Eng Process 2004;43:1115–1127.
45. Wakamatsu Y, Matsumoto H, Minagawa M, Tanioka A. J Colloid Interface Sci 2006;
300:42–445.
46. Xu C-X, Chen R-Y, Zheng X, Chen X, Chen Z. J Membr Sci 2008;307:218–224.
47. Xue Y, Wang N, Huang C, Cheng Y, Xu T. J Membr Sci 2009;344:129–135. and
48. Kumar M, Shahi VK. J Membr Sci 2010;349:130–137.
49. Kalsi PS. Spectroscopy of Organic Compounds. 2nd ed. New Age International Limited
Publication; 1996.
50. Oldani M, Schock G. J Membr Sci 1989;43:243–258.

51. Campbell P, Srinivasan R, Knoell T, Phipps D, Ishida K, Safarik J, Cormack T, Ridgway H.
Biotechnol Bioeng 1999;64:527–544.
52. Mulder M. Basic Principles of Membrane Technology. Netherlands: Kluwer Academic Pub-
lishers; 1996.
53. Jacobsen NE. NMR Spectroscopy Explained: Simplified Theory, Applications and Examples
for Organic Chemistry and Structural Biology. Hoboken (NJ): John Wiley and Sons, Inc.;
2007.
54. Dlugolecki P, Ogonowski P, Metz SJ, Saakes M, Nijmeijer K, Wessling M. J Membr Sci
2010;349:369–379.
55. Barsoukov E, Macdonald JR. Impedance Spectroscopy Theory, Experiment, and Applications.
2nd ed. Hoboken (NJ): John Wiley and Sons, Inc.; 2005.
56. Chilcott TC, Chan M, Gaedt L, Nantawisarakul T, Fane AG, Coster HGL. J Membr Sci
2002;195:153–167.
57. Chilcott TC, Coster HGL, George EP. J Membr Sci 1995;108:185–197.
58. Vanden PG, Mathot VBF. Thermochim Acta 2007;461:107–121.
59. Chakrabarty T, Rajesh AM, Jasti A, Thakur AK, Singh AK, Prakash S, Kulshrestha V, Shahi
VK. Desalination 2011;282:2–8.
60. Singh AK, Prakash S, Kulshrestha V, Shahi VK. ACS Appl Mater Interfaces 2012;
4:1683–1692.
61. Fontyn M, Bijsterbosch BH, Vant RK. J Membr Sci 1988;36:141–145.
62. Gohil GS, Shahi VK, Rangarajan R. J Membr Sci 2004;240:211–219.
63. Wu Y, Wu C, Xu T, Fu Y. J Membr Sci 2009;329:236–245.
64. Gottlieb MH, Neihof R, Sollner K. J Phys Chem 1957;61:154–159.
65. Spiegler KS, Wyllie MRJ. Physical Technique in Biological Research. Volume 2. New York:
Academic press; 1956.
66. Nadh JS, Muralidhara HS. Ind Eng Chem Res 1996;35:1133–1140.
67. Lakshminarayaiah N. Transport Phenomena in Membranes. London: Academic Press; 1969.
68. Balster J, Yildirim MH, Stamatialis DF, Ibanez R, Lammertink RGH, Jordan V, Wessling M.
J Phys Chem B 2007;111:2152–2165.
69. Saxena A, Kumar A, Shahi VK. J Colloid Interface Sci 2006;303:484–493.
70. Shaposhnik VA, Eliseeva TV. J Membr Sci 1999;161:223–228.
71. Jakobsen MR, Rasmussen JF, Nielsen S, Ottosen LM. J Hazard Mater 2004;106B:127–132.
72. Nagatani T, Yoshkawa N. J Membr Sci 2006;275:37–45.
73. Cifuentes L, Garcia I, Arriagada P, Casas JM. Sep Purif Technol 2009;68:105–108.
74. Smara A, Delimi R, Poinsignon C, Sandeaux J. Sep Purif Technol 2005;44:271–277.
75. Rahman U, Abo-Ghander NS, Zaidi SMJ. US patent 0219574A1S. 2006.
76. Gohil GS, Binsu VV, Shahi VK. J Membr Sci 2006;280:210–218.
77. Gohil GS, Nagarale RK, Binsu VV, Shahi VK. J Colloid Interface Sci 2006;298:845–853.
78. Saxena A, Kumar M, Shahi VK. J Colloid Interface Sci 2006;303:484–493.
79. Amado FDR, Rodrigues MAS, Morisso FDP, Bernardes AM, Ferreira JZ, Ferreira CA. J
Colloid Interface Sci 2008;320:52–61.
80. Reddy KJ, Sullivan BP, Bowen JM. Water Res 2003;37:2512–2519.
81. Kabay N, Yuksel M, Samatya S, Arar O, Yuksel U. Sep Sci Technol 2007;42:2615–2627.
82. Kabay N, Arar O, Samatya S, Yuksel U, Yuksel M. J Hazard Mater 2008;153:
107–113.
83. Lahnid S, Tahaikt M, Elaroui K, Idrissi I, Hafsi M, Laaziz I, Amor Z, Tiyal F, Elmidaoui A.
Desalination 2008;230:213–219.
84. Tahaikt M, Achary I, Menkouchi SMA, Amor Z, Taky M, Alami A, Boughriba A, Hafsi M,
Elmidaoui A. Desalination 2006;189:215–220.
85. Arar O, Yavuz E, Yuksel U, Kabay N. Sep Sci Technol 2009;44:1562–1573.
86. Wang DM, Huang CP. Sep Purif Technol 2008;59:333–341.
87. Xing Y, Chen X, Yao P, Wang D. Sep Purif Technol 2009;67:123–126.
88. Bergmann MEH, Iourtchouk T, Rittel AH. Electrochim Acta 2009;54:2417–2424.
89. Dermentzis K. J Hazard Mater 2010;173:647–652.
90. Grabows A, Zhang G, Strathmann H, Eigenberger G. J Membr Sci 2006;281:297–306.
91. Koter S, Warszawski A. Desalination 2006;198:111–123.
92. Ali MAB, Rakib M, Laborie S, Viers P, Durand G. J Membr Sci 2004;244:89–96.
93. Raissouni I, Marraha M, Azmani A. Desalination 2007;208:62–72.
94. Kumar M, Tripathi BP, Shahi VK. J Chem Technol Biotechnol 2010;85:648–657.
95. Eliseeva TV, Shaposhnik VA, Krisilova EV, Bukhovets AE. Desalination 2009;241:86–90.
96. Lee H-J, Oh S-J, Moon S-H. Water Res 2003;37:1091–1099.
97. Aghajanyan AE, Hambardzumyan AA, Vardanyan AA, Saghiyan AS. Desalination 2008;
228:237–244.
98. Min-tian G, Koide M, Gotou R, Takanashi H, Hirata M, Hano T. Process Biochem 2005;
40:1033–1036.
99. Baudry MR, Chaufer B, Lucas D, Michel F. J Membr Sci 2001;184:137–148.
100. Bazinet L, Firdaous L. Biotechnology 2009;3:361–372.
101. Labbe D, Bazinet L. J Membr Sci 2006;275:220–228.
102. Aider M, Brunet S, Bazinet L. J Membr Sci 2008;309:222–232.
103. Firdaous L, Dhulster P, Amiot J, Gaudreau A, Lecouturier D, Kapel R, Lutin F, Vezina L-P,
Bazinet L. J Membr Sci 2009;329:60–67.
104. Poulin J-F, Amiot J, Bazinet L. J Biotechnol 2006;123:314–328.
105. Poulin J-F, Amiot J, Bazinet L. J Membr Sci 2007;299:83–90.
106. Aider M, Brunet S, Bazinet L. Sep Purif Technol 2009;69:63–70.
107. Veerman J, Saakes M, Metz SJ, Harmsen GJ. J Membr Sci 2009;327:136–144.
108. Wang ZX, Luo YB, Yu P. J Membr Sci 2006;280:134–137.
109. Koter S. Sep Purif Technol 2008;60:251–258.
110. Saxena A, Gohil GS, Shahi VK. Ind Eng Chem Res 2007;46:1270–1276.
111. Kumar M, Saxena A, Shahi VK. Sep Sci Technol 2011;46:774–785.
112. Yi SS, Luand YC, Luo GS. J Membr Sci 2005;255:57–65.
113. Xu FN, Innocent C, Pourcelly G. Sep Purif Technol 2005;43:17–24.
114. Yi SS, Lu YC, Luo GS. Sep Purif Technol 2008;60:308–314.
115. Li H, Mustacchi R, Knowles CJ, Skibar W, Sunderland G, Dalrymple I, Jackman SA. Tetra-
hedron 2004;60:655–661.
116. Bouchoux A, Balmann HR, Lutin F. Sep Purif Technol 2006;52:266–273.
117. Zhang N, Peng S, Huang C, Xuand T, Li Y. J Membr Sci 2008;309:56–63.
118. Jaime-Ferrer JS, Couallier E, Viers P, Rakib M. J Membr Sci 2009;328:75–80.
119. van der Stegen JHG. The state of the art to modern chlor-alkali electrolysis with membrane
cells [PhD thesis]. University of Twente; 2000.
120. Faverjon F, Durand G, Rakib M. J Membr Sci 2006;284:323–330.
121. Yazicigil Z. Desalination 2007;212:70–78.
122. Shee FLT, Arul J, Brunet S, Bazinet L. J Membr Sci 2007;290:29–35.

123. Mier MP, Ibanez R, Ortiz I. Biochem Eng J 2008;40:304–311.
124. Shee FLT, Arul J, Brunet S, Bazinet L. J Agric Food Chem 2008;56:10019–10026.
125. Shee FLT, Bazinet L. J Membr Sci 2009;341:46–50.
126. Bazinet L, Pouliot Y, Castaigne F. J Membr Sci 2010;352:32–40.
127. Bazinet L, Ippersiel D, Mahdavi B. Innov Food Sci Emerg Technol 2004;5:17–19.
128. Bazinet L, Ippersiel D, Mahdavi B. J Agric Food Chem 2004;52:1980–1984.
129. Shee FLT, Angers P, Bazinet L. J Agric Food Chem 2005;53:5635–5639.
130. Shee FLT, Angers P, Bazinet L. J Membr Sci 2005;262:100–106.
131. Stancheva KA. Appl Dial Oxide Commun 2008;31:758–775.
132. Xu TW. J Membr Sci 2005;263:1–29.
133. Xu TW. Resour Conserv Recy 2002;37:1–22.
134. Luo AP, Wang XC. J WUYI Univ (Nat Sci Ed) 2000;14:29–32.
135. Jeong JK, Kim MS, Kim BS. J Hazard Mater 2005;124:230–235.
136. Xu TW, Yang WH. J Hazard Mater 2004;109:157–164.
137. Lin SH, Lo MC. J Hazard Mater 1998;60:247–257.
138. Palaty’ Z, Zakova A. Desalination 2004;169:277–285.
139. Tang JJ, Zhou KG, Zhang QX. Trans Nonferr Metal Soc 2006;16:951–955.
140. Tang JJ, Chen JJ, Zhang W, Zhou KG, Zhang QX. Membr Sci Technol 2005;25:50–53.
141. Zhao YJ, Xing WH, Xu NP. J Chem Eng Chinese Univ 2002;16:217–221.
142. Li XB, Wei C, Deng ZG, Li MT, Li CX. Chin J Nonferr Metals 2008;18:88–91.
143. Xu TW, Yang WH. J Membr Sci 2001;183:193–200.
144. Xu TW, Yang WH, Liu ZM. Techno Water Treat 1999;25:204–208.
145. Wang J. Environ Sci Manage 2005;30:45–51.
146. Zhai JW, Wang WZ, An XC, Jiao GL. Membr Sci Technol 2003;23:18–20.
147. Li HB, Niu YQ, Huang CY, Yu XH. Uranium Min Metall 2005;24:23–27.
148. Wei C, Li XB, Deng ZG, Fan G, Li MT, Li CX. J Hazard Mater 2010;176:226–230.
149. Xu J, Fu D, Lu S. Sep Purif Technol 2009;69:168–173.
150. Kang MS, Yoo KS, Oh SJ, Moon SH. J Membr Sci 2001;188:61–70.
151. Palaty Z, Zakova A. Sep Sci Technol 2007;42:1965–1983.
152. Palaty Z, Bendová H. Sep Purif Technol 2009;66:45–50.
153. Xu J, Lu S, Fu D. J Hazard Mater 2009;165:832–837.
154. Bendová H, Palaty Z, Záková A. Desalination 2009;240:333–340.
155. Xu TW, Yang WH. J Membr Sci 2003;220:89–95.
156. Zhang HM, Li DL, Li DB, Cao S, You LJ. Membr Sci Technol 2006;26:86–89.
157. Zheleznov A, Windmoller D, Korner S, Boddeker KW. J Membr Sci 1998;139:137–143.
158. Palaty Z, Stocek P, Zakova A, Bendova H. J Appl Polym Sci 2007;106:909–916.
159. Narebska A, Staniszewski M. Sep Sci Technol 2008;43:490–501.
160. Narebska A, Staniszewski M. Sep Sci Technol 1997;32:1669–1682.
161. Palaty Z, Zakova A, Prchal P. Desalination 2007;216:345–355.
162. Palaty Z, Stocek P, Bendova H, Prchal P. Desalination 2009;243:65–73.
163. Zhang QX, Zhang CF. Membr Sci Technol 2001;21:37–43.
164. Kulprathipanja S. US patent 7,241,918. 2007.
165. Akgemci EG, Ersoz M, Atalay T. Sep Sci Technol 2004;39:165–184.
166. Noma Y. Water Treat 1995;21:267–270.

167. Yang J, Liu KC, Guo R, Peng J, Xu DC. Environ Chem 2006;25:629–632.
168. He SY, Liu M. Chin Resour Compr Util 2005;6:13–16.
169. Zhang QX, Xiao LS. Chin J Rare Metals 2003;27:1–7.
170. Elmidaoui A, Cherif AT, Molenat J, Gavach C. Desalination 1995;101:39–46.
171. Sarkar S, Sengupta PK, Prakash P. Environ Sci Technol 2010;44:1161–1166.
172. Strathmann H. Desalination 2010;264:268–288.

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ELECTRO-MEMBRANE PROCESSES

Ajay K. Singh and Vinod K. Shahi

Currently, electromembrane separation processes such as electrolysis, electrodialysis

+ – Fixed ionic groups

FIGURE 1 Schematic presentation of (a) CEM and (b) AEM.

Desired membranes properties can be controlled by functionalization of base

2 RECENT DEVELOPMENTS IN ION-EXCHANGE MEMBRANES (IEMs)

2.1 Heterogeneous Ion-Exchange Membranes

2.2 Homogeneous Ion-Exchange Membranes

Where R1: sulfonated diamine; R2: nonsulfonated diamines

FIGURE 2 Reaction route for the synthesis of sulfonated polyimides.

FIGURE 3 Reaction route for the sulfonation of poly(ether sulfone) (PES).

2.3 Organic–Inorganic Hybrid Ion-Exchange Membrane

CH3 CH3 CH3

CH CH2 CH CH2 CH CH2 CH CH2

HS Si Si SH H2O2 HO3S Si Si SO3H

FIGURE 6 Schematic reaction route for the preparation of organic–inorganic nanocomposite

2.4 Bipolar Membranes (BPMs)

3 CHARACTERIZATION OF ION-EXCHANGE MEMBRANES

3.1 Spectroscopic Characterization

3.1.1 Fourier Transform Infrared (FT-IR) Spectrophotometry. FT-IR is generally

3.1.2 Attenuated Total Reflection–Fourier Transform Infrared Spectroscopy (ATR-

3.1.3 Nuclear Magnetic Resonance (NMR) Spectroscopy. NMR is a spectroscopic

FIGURE 9 Schematic diagram of flow-cell operation in ATR-FTIR.

0.00 7.80 7.60 7.40 7.20 7.00 6.80

number of residual hydrogen atoms (HA,A B ,B ,C ,D ), the degree of sulfonation of SPES

3.1.4 Electrochemical Impedance Spectroscopy (EIS). It is a powerful technique for

3.1.5 Thermal Analysis of Ion-Exchange Membranes. The term thermal analysis

3.1.6 Thermal Gravimetric Analysis (TGA). TGA is a simple analytical technique

FIGURE 12 Equivalent circuit for the ion-exchange membrane with solution.

Weight loss (%)

FIGURE 13 Schematic representation of a TGA curve for a membrane.

a dynamic mode of operation. A representative of TGA curve for a membrane is shown

1. Thermal Stability. Related materials can be compared at elevated temperatures

(Mettler Toledo TGA/SDTA851e with stare software) under nitrogen atmosphere

3.1.7 Differential Scanning Calorimetry (DSC). DSC is an effective analytical tool

FIGURE 14 Schematic representation of DSC curve for a membrane.

FIGURE 15 Dynamic mechanical analysis of different hybrid nanofiltration (NF) membranes.

3.2 Physicochemical Characterization of the Ion-Exchanged Membranes

3.2.2 Determination of Ion-Exchange Capacity (IEC). IEC is defined as the ratio

3.3 Electrochemical Characterization

3.3.1 Membrane Potential Measurements. It is observed that when a membrane sep-

Reference Solution 1 Membrane Solution 2 Reference

Electrode potential Electrode potential

FIGURE 16 Schematic diagram for membrane potential measurements.

FIGURE 17 Schematic experimental setup for the determination of membrane permselectivity

3.3.2 Membrane Permselectivity Measurements. It is an important parameter that

3.3.3 Electroosmotic Permeability Measurements. If an electric field is applied to the

FIGURE 19 Schematic diagram of the experimental setup for electroosmotic study.

where L12 is electroosmotic permeability of the charged membranes (A−1 cm s−1 ), J

3.3.4 Membrane Conductivity Measurements. Conductivity is related to the electrical

4 ELECTROMEMBRANE PROCESSES BASED ON IEMs

4.1 General Description and Application of ED

At the cathode, 2e− + 2H2 O = H2 (g) + 2OH−

Diluted compartment (DC) Concentrated compartment (DC)

Cation Anion-exchange membrane

FIGURE 21 Schematic representation of the principle of electrodialysis. (Please refer to the

4.1.1 Electrochemical Process for Water Purification.

Cation Anion-exchange membrane

4.1.1.3 Electro-Electrodialysis (EED) for Chromic Acid Recovery from Wastewater. An

4.1.1.4 Electrodeionization (EDI) for Ultrapure Water. Electrodeionization (EDI) is a

Concentrating Diluting Concentrating

Concentrate Product Concentrate