i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 8 8 6 8 e8 8 7 5

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EIS studies on electro-electrodialysis cell for concentration

of hydriodic acid

Pradeep Kumar Sow, Sonal Sant, Anupam Shukla*

Department of Chemical Engineering, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110010, India

article info abstract

Article history: EIS studies were carried out on an electro-electrodialytic cell used for concentration of
Received 28 April 2010 hydriodic acid using platinum electrodes and nafion117 membrane. Different impedance
Received in revised form spectra were obtained where the concentration of iodine was varied while the concen-
10 June 2010 tration of HI was kept fixed at 55 wt%. Equivalent circuit model was used to simulate the
Accepted 13 June 2010 experimental data and it was found that the impedance of the cell without membrane can
Available online 16 July 2010 be modeled using a single Warburg element along with ohmic resistance in series. This
indicates presence of only diffusion transport resistance at the electrode and absence of
Keywords: any non-electroneutral layer. The impedance spectra for cell with membrane can be
EIS modeled using a Warburg element and a CPE with capacitive character along with ohmic
Hydriodic acid resistance in series. This indicates formation of a non-electroneutral (heterogeneous
Iodine transport) layer at the membrane in addition to a diffusion transport layer. It was found
Electro-electrodialysis that the ohmic resistance increased with increase in the concentration of iodine while the
impedances due Warburg and heterogeneous transport layer decreased with increase in
iodine concentration.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction IS cycle comprises of the following reactions [5]:

393 K
Hydrogen has emerged as one of the most promising Bunsen reaction: I2 ðlÞ þ SO2 ðgÞ þ 2H2 OðlÞ ! 2HIðaq:Þ
secondary energy carrier for mobile and remote power þ H2 SO4 ðaq:Þ (1)
requirements [1,2]. Hydrogen is not available in free form
but it can be produced from abundantly available water, 1123 K
Sulphuric acid decomposition: H2 SO4 ðaq:Þ ! H2 OðlÞ
which is a renewable resource. Thermochemical water
decomposition cycles for hydrogen generation have been þ SO2 ðgÞ þ ð1=2ÞO2 (2)
an attractive option since their advent in 1970s. Out of
723 K
those, Iodineesulphur (IS) process studied by general Hydrogen iodide decomposition: 2HIðaq:Þ ! H2 þ I2 ðlÞ (3)
atomics has been one of the most promising [3]. These
In the traditional IS cycle, the Bunsen reaction is carried out
cycles decompose water by application of heat at temper-
by direct contact of sulphur dioxide, water and iodine where
atures lower than its direct decomposition temperature
an excess amount of water and iodine are used for high
which is made possible by using certain chemicals as
conversion and separation of the two acid phases [6]. Tradi-
recycling agents [4].
tional cycle has low thermal efficiency primarily because of

* Corresponding author. Tel.: þ91 11 26596290; fax: þ91 11 26581120.

E-mail address: anupam@chemical.iitd.ac.in (A. Shukla).
0360-3199/$ e see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.06.031
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 8 8 6 8 e8 8 7 5 8869

Impedance
Analyser
a

Electrode
Electrode

Cation
exchange
membrane

Fig. 1 e A schematic diagram of the EED cell used for

impedance measurements. The measurements are taken
by filling electrolyte solution (in batch mode) and without
stirring.
b

use of excess amount of water and iodine. An excess amount

of iodine leads to pseudo- azeotropic HIx solution (molar ratio
of HI: H2O ¼ 1:5) whose further concentration using distilla-
tion requires large amount of heat [7,8]. One of the suggested
ways to get over this difficulty is to use electro-electrodialysis
(EED) to concentrate the HIx solution coming out of Bunsen
reactor beyond its azeotropic composition [9]. Feasibility of
operating Bunsen reaction above azeotropic concentration of
HIx mixture is also reported in the literature [10].
An EED cell essentially consists of two compartments, both
containing HIx solution, separated by a cation exchange
membrane and the following iodineeiodide redox reaction
takes place at the electrodes in the two compartments of the Fig. 2 e Measured impedance response of the EED cell for
cell [4,8,11]: solution C (3 M iodine in 55 wt% HI) represented using (a)
Bode plot; and (b) Nyquist plot.
cathode
I2 þ 2e % 2I (4)
anode

The cation exchange membrane allows selective perme-

ation of the proton from anode to cathode compartment and it
leads to increase in the concentration of HI in the catholyte
and depletion of its concentration in the anolyte. Since electric
power is used to run the EED cell its efficiency has consider-
able effect on the overall thermal efficiency of the IS process. It
is therefore necessary to understand the various transport
and other electric resistances in an EED cell for the optimi-
zation of the EED process and so overall efficiency of the IS
cycle. One of the ways to characterize the transport resis-
tances of EED cell is to use electrochemical impedance spec-
troscopy (EIS) and interpret the data in terms of various circuit
elements (like resistance, capacitors etc.) to represent the
different transport phenomena occurring inside the EED cell
system.
EIS is a powerful noninvasive tool for investigation of
electrochemical systems. EIS technique has been used in
various fields of electrochemistry for characterizing transport
properties and electrical inhomogeneities of the systems
[12e16]. EIS technique helps to separate out process that
occurs simultaneously in time domain on basis of relative
dominance at various frequency ranges. EIS has already been
used for ion exchange membrane (IEM) systems for under-
standing the resistance to transport of ions through the IEM
system in various frequency domains [17e20]. In EIS, imped-
ance response of the system to alternating voltage or current
signal is used to separate out various phenomena (like
heterogeneous transport (HT), diffusion boundary layer (DBL),
solution resistance etc) which dominate the total impedance
in different frequency ranges.
In the present work, we have used EIS technique to
investigate the transport resistances of an EED cell used for
concentration of HIx solution. The cell consists of anode and
cathode compartments separated by Nafion 117 membrane
and Platinum electrodes in both the compartments. In all the
experiments, the anolyte and catholyte solutions were iden-
tical and contained 55 wt% HI solutions with different amount
of iodine in different runs. The concentration of iodine was
varied in the range of 0.5e4 M. In addition impedance spectra
were also taken for an EED cell without membrane to inde-
pendently determine the impedance response of the elec-
trodes. Equivalent circuit model was used to simulate the
impedance response of cell.
8870 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 8 8 6 8 e8 8 7 5

0.5
-1 With Membrane
Without Membrane
-2
0.4

-3 Slope ~ 0.5

ln(-Zimag)
0.3 -4
(Ω )

-5
0.2
Solution A -6 Slope ~ 1
Solution B
Solution C -7
0.1
Solution D
-8

0.0
-6 -4 -2 0 2 4 6 8 10 12
1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 ln (ω )
(Ω )
Fig. 5 e ln(LIm(Z )) vs. ln(u) for cell with and without
Fig. 3 e Nyquist plot representation of the impedance membrane containing solution C (3 M iodine in 55 wt% HI).
responses of the EED cell with membrane and containing Unfilled symbols represent impedance data for the cell
55 wt% HI and different concentration of iodine. Symbols without membrane and the filled symbols represent
represent the measured impedance data and the solid impedance data for the cell with membrane. For both the
curves represent the simulated values of the equivalent cases, linear variation of slope close to L0.5 shows presence
circuit. of the diffusion boundary layer or the Warburg behavior. For
cell with membrane, two linear regions are seen with one at
high frequency region having slope near L1 and the other at
lower frequencies having slope near L0.5.
2. Theory

2.1. Overview of EIS

In EIS measurements the complex impedance response of an
electrochemical cell is determined over a range of frequencies
using a perturbed voltage or current signal. The results of the
impedance study are generally represented in terms of
a nyquist plot where the imaginary part of the impedance is
0.5
0.4
0.3
-Zimag(Ω )
plotted against the real part [12,13]. Nyquist plots suffer from
a major disadvantage that the frequency is not shown in the
plots. Other type of representations like bode plots where
overall impedance and the phase angle is plotted against the
frequency and cole-cole plots where square of the real and the
imaginary parts of the measured impedance are plotted
against each other also exist [16]. In real systems the overall
impedance of the system is a function of more than one cell
element, but their relative magnitudes changes strongly with
change in the frequency of the signal. At very high frequency
all the capacitive impedance becomes negligible and the total
impedance of the cell corresponds to the ohmic resistance.
The region where the imaginary component of the impedance
is not negligible can again be divided into two regions. The

high frequency region (generally >100 Hz) is dominated by the

charge transfer or the heterogeneous transport and the low
0.2 frequency range (<0.1 Hz) is generally dominated by the mass
Solution A transfer or the diffusion of the species over electroneutral
Solution B
boundary layers.
Solution C
0.1 Impedance spectra are understood either by simulating
Solution D
a complete process model of the system or by representing
the system as an equivalent circuit. Though the first
0.0
1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 approach is more rigorous, equivalent circuit modeling is
Zreal(Ω ) simpler and can help find the various impedances i.e.,
transport resistances present in the system. An equivalent
Fig. 4 e Nyquist plot representation of the impedance circuit comprising of the electrical elements like capacitor,
responses of the EED cell without membrane and resistor, and constant phase elements is proposed and
containing 55 wt% HI and different concentration of iodine. arranged in a logical order either connecting them in series
Symbols represent the measured impedance data and the or in parallel which best represents the transport processes
solid curves represent the simulated values of the (mass transfer, charge transfer, etc.) of the electrochemical
equivalent circuit. cell.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 8 8 6 8 e8 8 7 5 8871

a b Impedance response of the cell can be modeled with an

equivalent circuit containing a combination of circuit
I2 I2
elements where each element represents a resistance to the
I-
transport of ions in the cell. The ohmic resistance to transport
I2 I2
of ions is modeled as a resistor, while the others resistances
I- like DBL are represented using a parallel combination of
I2 I2 a resistance (R) and a constant phase element (CPE). In
I- general, use of constant phase element gives better match
I2 I2 with experimental data as compared to use of simple
I- elements like capacitor because in real system the capacitive
I2 I2 elements or current are spatially distributed. For the region
where the imaginary part of the impedance has negative
values, the impedance of the CPE [18] can be expressed as:
Electrodes at high and Diffusion Boundary layer at the
n
medium frequency cathode observed at low frequency. ImðZÞ ¼ Y0  ðjuÞ (6)
n
where Y0 is the admittance (U/s ) and n is the empirical
c I- I- parameter with value between 0 and 1. This value of n deter-
I2
mines the nature of CPE. When n is close to a value of 0.5 the
I -
I- CPE is called Warburg impedance and corresponds to diffu-
sion resistance. For n value close to 1 and 1 CPE represents
I2
capacitance and inductance, respectively. In many instances,
I- I-
there exist frequency regimes where only one of the circuit
I2 elements of the total equivalent circuit dominates. In such
I- I- case it is possible to identify these regions and also the value
I2 of n by plotting imaginary part of impedance with frequency
I- I- on a log-log plot (ln(Im(Z )) v/s ln(u)).

Diffusion Boundary layer at the 3. Experimental

anode observed at low frequency.
Fig. 6 e A schematic representation of the various
transport phenomena occurring at different frequency
ranges at the electrode (a) electrode at very high frequency
(b) formation of diffusion boundary layer (DBL) at the
cathode (c) formation of DBL at the anode. The DBL region
is electroneutral, however HD ions present along with IL
ions are not shown for simplicity.
2.2. IEM system
The behavior of the IEM systems can be explained in the terms
of the complex conductivity. As shown in Eqn. (5), this
complex conductivity term can be expressed in the terms of
conductivity (s) and the dielectric permittivity (3) which arises
due to diffusion or mass transfer and charge accumulation,
respectively [17,18].
s ¼ s þ ju3 (5)
pffiffiffiffiffiffiffi
where j ¼ 1
From the equation we can see that the complex conduc-
tivity term is dominated by the conductivity term at low
frequency (u < s/3) and similarly at high frequency (u > s/3) the
complex conductivity term is dominated by the dielectric
permittivity term. A spatial dispersion of the imposed current
occurs in many systems and is due to the two phenomena of
which one is due to the DBL at lower frequency and the other
is the space charge layer (also called as heterogeneous trans-
port, HT) at higher frequency.
All the impedance measurements were performed on a two-
compartment electrochemical cell (shown schematically in
Fig. 1), made up of teflon with a compartment volume of 12 ml
each and platinum electrodes. Nafion 117 membrane supplied
by Electrochem Inc. (USA) was placed between the two
compartments with active area of about 5 cm2. Electrolyte
solutions were prepared using 55 wt% hydroiodic acid
supplied by Merck specialties Pvt. Ltd., and iodine supplied by
Fischer Chemicals Ltd. without any further purification. In all
the experiments, concentration of HI was kept at 55 wt% while
the concentration of iodine in the solution was varied in the
range of 0.5e4 M. All the experiments were conducted at
22  1  C with electrochemical cell in batch mode without
stirring.
All the impedance measurements were done with a per-
turbed sinusoidal ac voltage signal of amplitude 5 mV in the
frequency range of 4 kHze3 mHz using a potentiostat/galva-
nostat/ZRA (Gamry Instruments Inc, Model- Reference 600).
The impedance data obtained as nyquist and bode plots is
used for analysis.
4. Results and discussion
Initially the measurements were carried out in a cell made up
of plexiglass and after a few runs the plexiglass endplates
were found to be intercalated with iodine which resulted in
change in the concentration of the iodine while the
measurements were being taken. In view of this a cell made
8872 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 8 8 6 8 e8 8 7 5
up of teflon was fabricated and subjected to the iodine envi-
ronment. No intercalation of iodine was observed and all
impedance measurements reported in this study were taken
using a two-compartment teflon cell without stirring. In order
to improve thermal efficiency of IS cycle newer ways of
carrying out Bunsen reaction are being explored where the
aim is to reduce excess water and iodine used in the tradi-
tional scheme [21]. Membrane electrolysis for Bunsen reaction
is reported in literature where the I2/HI ratio near and less
than 1 are used [22]. Even with traditional scheme, it is
possible to remove iodine by flash/simple distillation till the
amount of iodine is sufficiently reduced [23]. In view of this,
electrolyte solution with I2/HI ratio less than 1 was used for
impedance measurements. In all, eight impedance measure-
ments were taken; four on cell with membrane and four on
cell without membrane. In all the runs, the HI concentration
was 55 wt%. The iodine concentration in the set of four runs
was 0.5, 2, 3 and 4 M which are hereafter referred to as A, B, C
and D solutions, respectively. Impedance measurement on
cell without membrane was done to separately obtain the
impedance response of the cell with electrodes alone. It hel-
ped in identification of the impedance components due to the
membrane and the ones due to the two electrodes.
4.1. General trend of an impedance spectrum
Fig. 2 shows impedance response of the cell with membrane
in solution C using nyquist and bode plots. Bode plot (Fig. 2a)
shows that magnitude of impedance is nearly constant at high
frequency (103e100 Hz) and the phase angle in this range is
nearly zero. The magnitude of impedance at zero phase angle
provides value of the combined solution and membrane
resistance [24]. The nyquist plot (Fig. 2b) shows a capacitive
a RDBL
RS
Solution
b RSM
RHT
QHT
RSM
Solution Heterogeneous
+Membrane Transport
Fig. 7 e Equivalent circuit for the EED cell system (a) without membrane consists of two parts one for the solution resistance
and other for the diffusion boundary layer (b) with membrane which consist of 3 parts: resistance due to solution and
membrane (RSM), heterogeneous transport part, and the diffusion boundary layer.
loop. As shown in Fig. 3, similar qualitative behavior is shown
by the measured impedance responses of all the solutions and
the radius of capacitive loop of nyquist plot is found to
decrease with increase in iodine concentration. Also it can be
seen from the figure that the ohmic resistance of the cell
(value of x-axis intercept) increases with increase in the
concentration of iodine. Different transport resistances in the
cell can be identified by a quantitative simulation of imped-
ance response using equivalent circuit modeling. Fig. 4 shows
the impedance response in form of nyquist plots for the cell
without membrane for electrolyte solutions with different
iodine concentration. It may be seen from the figure that
ohmic resistance of the cell increases with increase in iodine
concentration. Also all the plots show capacitive loop and the
diameter of the loop increases with increase in iodine
concentration.
4.2. Equivalent circuit of IEM system
For the cell without membrane containing solution C, unfilled
symbols of Fig. 5 shows variation of ln(ImZ) with ln(u). It can
be seen from the figure that except at very high frequency
range the ln(Im(Z )) varies linearly with ln(u) and the value of
slope is close to 0.5 which corresponds to a Warburg
impedance arising due to diffusion transport resistance. Fig. 6
shows a schematic of the iodine/iodide distribution near
electrode that corresponds to development of a diffusion
boundary layer. As shown in Fig. 6, DBL formation is expected
to occur at both the electrodes; however, the data in Fig. 5
suggests that single Warburg impedance can be used to
model the transport resistance due to the two DBLs at the two
electrodes. Thus the equivalent circuit (Fig. 7a) for the cell
without membrane consists of two elements; a resistance (Rs)
QDBL
Diffusional
Boundary
Layer
RDBL
QDBL
Diffusional
Boundary Layer
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 8 8 6 8 e8 8 7 5
in series with a circuit element made up of a parallel combi-
nation of a resistor and a Warburg impedance element. The Rs
represents the ohmic resistance of the cell due to solution.
The other part of the equivalent circuit consisting of a resistor
(represented as RDBL) in parallel with an element of admit-
tance QDBL is used to model the Warburg impedance. Value of
Rs was determined from the high frequency region of the bode
plot. Least square fitting of experimental data with the
simulated values of the equivalent circuit was used to deter-
mine the values of the other circuit elements. Similar
impedance behavior is shown by cell without membrane for
other solutions also and their impedance data is also modeled
using similar equivalent circuit. Fig. 4 shows that the simu-
lated values (solid curves) matched well with the experi-
mentally measured values (symbols).
Filled symbols in Fig. 5 shows a plot of ln(Im(Z )) v/s ln(u) for
cell with membrane containing solution C. It can be seen from the
figure that there are two distinct regions were ln(Im(Z )) varies
linearly with ln(u). The region at lower frequency has slope close
to 0.5 corresponding to Warburg impedance behavior while the
one at higher frequency region has slope close to 1 corre-
sponding to capacitive behavior. It has been reported in literature
[18] that impedance spectra of IEM systems show a Warburg
impedance dominant region along with a region dominated by
impedance of the capacitive behavior.
Transport of iodine and iodide species occurs near the two
electrodes and the diffusion boundary layer near electrodes
refers to resistance to transport of these species. Near
membrane transport of Hþ ions occurs and the diffusion
boundary layer near the membrane refers to resistance to
transport of Hþ ions. However, Fig. 5 shows that in cell with
membrane also, single linear region of dominant Warburg
impedance exists. This indicate that just as for the cell
without membrane where the two DBLs, one at each elec-
trode, can be modeled using one Warburg impedance so also
for the cell with membrane the multiple DBLs can be modeled
using single Warburg impedance. The impedance of capaci-
tive nature is attributed to the thin space charge region at the
membrane. This is also referred to as impedance due to
heterogeneous transport. Fig. 8 shows a schematic view of the
relative location and distribution of charges corresponding to
the transport resistances at membrane described above. Thus
the equivalent circuit for cell with membrane (Fig. 7b) consists
of three circuit elements. These are a resistor (Rsm) for the
ohmic resistance of solution and membrane in series with two
other circuit elements. Each of these circuit elements consist
of parallel combination of a resistor and a CPE, one with n
close to 0.5 representing Warburg impedance and the one
with n close to 1 representing heterogeneous transport. The
Rsm value was determined from bode plot using impedance
value at zero phase angle. Other circuit element values were
obtained using least square fitting between the experimental
data and the one simulated using the equivalent circuit. Fig. 3
shows that the simulated values closely match the experi-
mental data.
4.3. Effect of iodine concentration
Plot of ln(Im(Z )) v/s ln(u) for solutions with different iodine
concentration showed behavior similar to the one described
8873
a b
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
Cation
Exchange Heterogeneous
Membrane transport layer
c
H+
H+
H+
H+
H+
H+
Diffusional Boundary
Layer at membrane
Fig. 8 e A schematic diagram of the various impedances for
the membrane acting in different frequency ranges (a) at
very high frequency shows only presence membrane
resistance; (b) at medium frequency shows the presence of
heterogeneous transport layer or the electrical double layer
which gives rise to the capacitive behavior; and (c) at low
frequency shows the presence of DBL which gives rise to
Warburg behavior.
above. Thus, their impedance response was modeled using
similar equivalent circuit and the best fit values of the various
circuit elements is given in Table 1 along with those for the cell
without membrane. It shows that the Rsm values for all the
solutions are close to the Rs value for same solution indicating
that membrane resistance is negligible compared to the
solution resistance. Also the values of Rs and Rsm increase
with increase in the iodine concentration. For the case of cell
without membrane, it may be seen from the Table that the
admittance due to DBL (Warburg element) decreases with
increase in the concentration of iodine. For the case of cell
with membrane, the admittance due to DBL (Warburg
element) is found to increase with increase in iodine
concentration. Also a similar trend is also shown by admit-
tance due to heterogeneous transport layer for the cell with
membrane. A similar behavior is also reported in literature
[18] for an IEM system in KCl solution. It has been reported in
the literature that an increase in the I2/HI molar ratio causes
increase in proton transport number inside the membrane [8].
As protons transport is the dominant transport mechanism in
the membrane, the increase in transport number of proton
8874 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 8 8 6 8 e8 8 7 5

Table 1 e Impedance values of circuit elements in equivalent circuit used to model impedance response of the EED cell. The
values were obtained by using least square fitting of the experimentally measured impedance values.
Iodine Cell Impedance elements
concentration
(M) Rsm (U) Heterogeneous transport layer Diffusion boundary layer

RHT (U) QHT RDBL (U) QDBL

a
Y0,HT (S  s ) n Y0,DBL (S  sa) n

0.5 (A) With membrane 1.689 0.919 16.4 0.815 0.637 3.101 0.458
Without membrane 1.662 e e e 1.239 5.124 0.524
2 (B) With membrane 1.778 0.417 48.64 0.870 0.700 4.591 0.510
Without membrane 1.739 e e e 1.435 4.512 0.524
3 (C) With membrane 1.929 0.301 64.1 0.874 0.761 5.231 0.472
Without membrane 1.865 e e e 1.535 4.223 0.541
4 (D) With membrane 2.122 0.0993 122.4 0.972 1.14 5.659 0.454
Without membrane 2.051 e e e 1.981 3.842 0.499

leads to decrease in the impedance of the heterogeneous
layer. Also it is seen that for this system the, ohmic resistance
(Rsm) increases with increase in iodine concentration. Similar
trends have been reported in literature [8] where the cell
voltage was found to increase with increase in the iodine
concentration for the EED cell which is believed to be due to
increase in the solution resistance.
The main objective of the EED step in the IS process is
increasing the efficiency of the process by electrochemically
increasing the concentration of HI beyond its azeotropic
concentration. The results described above suggest that the
iodine concentration has considerable effect on the ohmic
resistance as well as on the admittance of the heterogeneous
transport layer. Optimizing iodine concentration is therefore,
needed for increasing the efficiency of the EED process itself.
From the results of EIS it can be seen that the iodine concen-
tration causes increase in the ohmic resistance of the solution
and increase in the admittance of heterogeneous transport
layer which corresponds to the proton conductivity of the
membrane. This suggests that HIx solution with very low or
high iodine concentration may not give minimum cell resis-
tance and the optimum level is in the intermediate iodine
concentration range. During the EED operation, iodine
concentration increases continuously in the anode compart-
ment and decrease in the cathode compartment. It has also
been reported in the literature cell voltage increase with time
of operation of an EED cell [8]. Above suggests that the oper-
ation should be run such that the iodine concentration does
not become too low in catholyte and too high in anolyte.
5. Conclusion
EIS studies were carried out on an electro-electrodialysis cell
used for concentration of hydriodic acid using platinum
electrodes and nafion117 membrane. Different impedance
spectra were obtained where the concentration of iodine was
varied while the concentration of HI was kept fixed at 55 wt%.
Equivalent circuit model was used to simulate the experi-
mental data and it was found that the impedance of cell
without membrane can be modeled using a single Warburg
element along with ohmic resistance in series. This indicates
presence of a diffusion transport resistance at the electrode
and absence of any space charge layer. The impedance
spectra for cell with membrane can be modeled using a War-
burg element and a CPE with capacitive character along with
ohmic resistance in series. This indicates formation of a non-
electroneutral heterogeneous transport layer at the
membrane in addition to a diffusion transport layer. It was
found that the ohmic resistance increased with increase in the
concentration of iodine while the impedances due Warburg
and heterogeneous transport layer decreased with increase in
iodine concentration.
Acknowledgement
Authors acknowledge the financial support from ONGC
Energy Centre for carrying out this work.
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