Research Article

ChemElectroChem doi.org/10.1002/celc.202200403

www.chemelectrochem.org

Determination of Ionic Diffusion Coefficients in Ion-

Exchange Membranes: Strong Electrolytes and Sulfates
with Dissociation Equilibria
Kuldeep,[a] José A. Manzanares,[b] Pertti Kauranen,[c] Seyedabolfazl Mousavihashemi,[a] and
Lasse Murtomäki*[a]
An Invited Contribution to the Hubert Girault Festschrift.

Ionic diffusion coefficients in the membrane are needed for the dissociation of bisulfate and NaSO4 , which makes the use of
modelling of ion transport in ion-exchange membranes (IEMs) the Nernst-Hartley equation, that is, splitting the electrolyte
with the Nernst-Planck equation. We have determined the ionic diffusion coefficient into its ionic contributions, impossible. The
diffusion coefficients of Na +, OH , H +, Cl , SO42 , NaSO4 , and expression of the diffusion coefficient of sulfates taking into
HSO4 from the diffusion experiments of dilute NaCl, NaOH, account the dissociation equilibrium has been derived and the
HCl, Na2SO4, and H2SO4 solutions through IEMs and the corresponding Fick equation has been integrated. In addition,
membrane conductivity measured in these solutions, using for sulfates, finite element simulations with COMSOL Multi-
electrochemical impedance spectroscopy. The order of diffusion physics, applying a homogeneous membrane model, were
fluxes across the anion-exchange membrane is found to be as done to give estimates of their ionic diffusion coefficients. This
H2SO4 > HCl > NaCl > Na2SO4 > NaOH, whereas for the cation- work offers a convenient approach to finding diffusion
exchange membrane it was NaOH > NaCl > Na2SO4 � H2SO4. coefficients of various ions inside IEMs.
Special attention is given to sulfates because of the partial

Introduction books.[10–12] Furthermore, a number of experimental techniques,

e.g., ion-exchange measurements,[13–16] conductivity,[17–21] radio-
Membrane separation processes are employed in the research labeled diffusion,[22–24] and Donnan dialysis[25] have also been
and applications of various wastewater treatment processes. used to measure the diffusion coefficients in IEMs.[26–28] All of
Examples of such include the usage of bipolar electrodialysis to these methods are applicable only for binary strong electro-
treat sodium sulfate stemming from the growing lithium-ion lytes. Modern techniques like NMR spectrometer diffusive units
battery industry,[1] reverse electrodialysis,[2] membrane-assisted can also measure self-diffusion coefficients for NMR active
capacitive deionization,[3] desalination and chemical recovery nuclei.[29] None of these methods are suitable to measure the
applications,[1,4] water electrolysis,[5] water-splitting in photo- diffusion coefficients of ions of weak electrolytes.
electrochemical cells,[6] and fuel cells.[7–9] Electrochemical impedance spectroscopy (EIS) can be used
A detailed theoretical study of ion transport inside the to determine the properties of an electrochemical system, and
membrane has already been published in various articles and complex mathematical expressions are often needed to explain
the impedance. The most straightforward application of EIS is
to determine the ohmic resistance of a system. When studying
[a] Kuldeep, Dr. S. Mousavihashemi, Prof. L. Murtomäki
membranes, EIS has been used to find out membrane
Department of Chemistry and Materials Science, School of Chemical
Engineering conditions,[30] conductivity,[31] transfer kinetics,[32] and fouling
Aalto University and scaling.[33,34] Nikonenko[32] et al. developed an equivalent
PO Box 1600, 00076 AALTO, Finland
circuit for the impedance of an ion-exchange membrane (IEM),
E-mail: lasse.murtomaki@aalto.fi
[b] Prof. J. A. Manzanares assuming that all ions had the same diffusion coefficients in the
Department of Thermodynamics aqueous and membrane phases.
University of Valencia
In our previous paper,[35] we reported studies of electro-
c/Dr. Moliner, 50. E-46100 Burjasot, Spain
[c] Prof. P. Kauranen diffusion across IEMs. Ionic diffusion coefficients were taken as
LUT University 10 % of their values in aqueous solutions at infinite dilution,
School of Energy Systems
except for H + for which it was 60 % of its aqueous value. These
P.O. Box 20, 53851 Lappeenranta, Finland
Supporting information for this article is available on the WWW under
values were chosen to fit experimental fluxes to Finite Element
https://doi.org/10.1002/celc.202200403 Method (FEM) simulations with COMSOL Multiphysics®. To
© 2022 The Authors. ChemElectroChem published by Wiley-VCH GmbH. This justify that choice, in this work we determine ionic diffusion
is an open access article under the terms of the Creative Commons coefficients in IEMs by combining membrane resistance meas-
Attribution Non-Commercial License, which permits use, distribution and
reproduction in any medium, provided the original work is properly cited urements with EIS and diffusion experiments of various strong
and is not used for commercial purposes. electrolytes. With partially dissociating electrolytes, H2SO4 and

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Na2SO4, this method does not apply as such, because there are F2 X 2
two measurements but three ions. Therefore, some assumption k¼ z Dc (3)
RT j j j j
must be done (see below), which naturally leaves some
uncertainty to the fitted values.
A homogeneous membrane model is applied, although is the electrical conductivity (Eq. (3)); f ¼ F=RT.
microscopic models have been presented in the literature.[11] Ions with an opposite charge to the IEM fixed charges are
The bottom line of the microscopic models – originating from called counterions (subscript ‘1’), and are the main charge
the Manning theory for counterion condensation in linear carriers via migration, while ions with the same charge, co-ions
polyelectrolytes with charge density above a critical value – is (subscript ‘2’) are transferred mainly by diffusion in the
that there exist two conducting phases, a compact phase interstitial space between the fixed charges. The concentration
composed of the counterions condensed on (or ion-paired to) of a binary electrolyte (subscript ‘12’) inside the IEM (superscript
the fixed-charge groups, and a diffuse electrical double layer M) is defined with the co-ion, Eq. (4):
around the charged linear polyelectrolytes. Ions in these two
phases would assume different mobilities. As appropriate and where ν2 is the stoichiometric coefficient of the co-ion in the
robust these models might be, they all suffer from the need of electrolyte. The flux density of a binary electrolyte across an IEM
introducing auxiliary variables, the values of which remain is given by Eq. (5):
merely unknown fitting parameters. Alternatively, an abun-
dance of sorption experiments, for example, with several dcM12
electrolytes at varying concentrations should be done; this JM12 ¼ DM12 (5)
dx
should be repeated when changing the membrane type.
Resorting to the homogeneous membrane model means that where
only one parameter, the fixed membrane charge that is usually
�
given by the manufacturer, is needed. This clearly underlines DM1 DM2 z21 cM1 þ z22 cM2
DM12 ¼ (6)
our engineering approach, i.e., the values given are averaged z21 DM1 cM1 þ z22 DM2 cM2
over several factors but represent – we believe – a reasonable
estimate for process design purposes. Furthermore, we wish to is its diffusion coefficient (Eq. (6)). In general, the electrolyte
show that with modern computational tools it is possible to diffusion coefficient DM12 is not really a meaningful quantity as it
have an easy access to the phenomena within a membrane that depends on the local concentrations. In neutral or very weakly
are otherwise hard to reach. charged membranes, DM12 is approximately equal to the Nernst-
Hartley diffusion coefficient n12 DM1 DM2 =ðn2 DM1 þ n1 DM2 Þ, where
n12 ¼ n1 þ n2 : In strongly-charged IEM, cM2 � cM1 and Eq. (6)
Theory reduces to DM12 � DM2 .
Eq. (5) can be integrated analytically after expressing DM12 as
There are a few ways to describe solute transfer in a solution, a function of cM2 only. Using the electroneutrality condition in
such as the theory of irreversible thermodynamics and Eq. (7).
phenomenological equations, the Fickian approach where
diffusion of neutral components is coupled with migration of z1 M
z1 cM1 þ z2 cM2 þ zM cM ¼ 0 () c þ cM2 þ X ¼ 0 (7)
charged species along their transport numbers, or the friction z2 1
coefficient (Stefan-Maxwell) approach.[10] Due to the lack of the
values of the transport parameters needed in these theories, to eliminate cM1 , where X ¼ zM cM =z2 > 0, Eq. (8) is reached:
the most common and practical approach is the Nernst-Planck
equation that implements the coupling of the ionic fluxes via � �
z1
T M1 cM2 1 z2 þ T M1 X z1 DM1
the local electroneutrality condition and the definition of DM12 ¼ ; T M1 ¼ : (8)
M M
electric current. c þT X
2
M
1 z1 D1 z2 DM2
The flux density of ionic species i is given by the Nernst-
Planck equation, Eq. (1): Integrating Eq. (5) with respect to cM2 , the electrolyte flux
density is given by Eq. (9):
� � � �
ti k d ln ci d� dci d�
ji ¼ RT þ z i F ¼ Di þ zi ci f (1) 8� �� � 9
z2i F2 dx dx dx dx > z1 >
> 1 cM2 ðhÞ cM2 ð0Þ >
M T1M < z2 =
J12 ¼ (9)
where Di is its diffusion coefficient, zi is its charge number, ci is > h
n2 h > �
z1
� i hM
c ðhÞþT M X >
i
>
:þ 1 1 T1M X ln c2M ð0ÞþT1M X ;
its molar concentration, z2 2 1

z2 D c where h is the membrane thickness. The concentration drop

ti ¼ P i 2i i (2)
j zj Dj cj cM2 ð0Þ cM2 ðhÞ inside the IEM is much smaller than the differ-
ence between the feed and receiver concentrations.
is its local transport number (Eq. (2)), and

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The conductivity of an IEM equilibrated with a binary c1 c3

electrolyte is given by Eq. (10): Kc ¼ : (15)
c2

F2 2 M M �
kM ¼ z D c þ z22 DM2 cM2 : (10)
The chemical potential of the electrolyte is given by Eq. (16):
RT 1 1 1

Hence, from Eqs. (9) and (10) and experimental measure- mS ¼ m1 þ m2 ¼ 2m1 þ m3 : (16)
ments of JM12 and kM , it is possible to calculate the diffusion
coefficients DM1 and DM2 , but it requires knowing the ionic In this work, the theoretical analysis of the diffusion
concentrations inside the IEM. experiments of H2SO4 and Na2SO4 has been done using two
It is commonly assumed that an equilibrium of distributing procedures. The first one consists of the numerical solution of
~wi ¼ m
ions prevails at the solution-membrane interface, i. e., m ~Mi , the ionic transport equations, Eq. (1), using COMSOL Multi-
even in the presence of electric current. Applying Guggen- physics simulations as described in detail in Ref [35]. The second
heim’s definition of the electrochemical potential, defined by procedure consists of deducing the Fick equation, Eq. (17):
Eq. (11):
dcS
JS ¼ DS (17)
~i ¼ m0i þ RT ln ai þ zi F�,
m (11) dx

the ionic concentration inside the IEM is now given by Eq. (12): for these electrolytes, and then numerically integrating Eq. (17).
In both cases, we have to take into account that the equilibrium
� 0;w � � �
gwi mi m0;M zi FD�D “constant” K c is a function of the electrolyte concentration,[37]
cMi ¼ cwi exp i
exp (12)
gMi RT RT because Eq. (15) is written in terms of the molar concentrations,
ci , rather than the ionic activities. We explain next the second
where γi’s refer to the activity coefficient and m0i the standard procedure.
chemical potential of species i; D�D ¼ �M �w is the Donnan In diffusion experiments the electric current density is zero,
P
potential. Similarly, since the chemical potential of a 1 : 1 0 ¼ i zi ji , and the (diffusion) electric potential gradient of
electrolyte is m12 ¼ m ~2 , its equilibrium condition at the
~1 þ m these ternary electrolytes is given by Eq. (18):
interface is,[37] given by Eq. (13):
� �
d� dm dm2 t3 dm3 dm2 t dmS
�
w 2 � 0;w � F ¼ t1 1 t2 þ ¼ þ t1 þ 3 ¼
�2 g � m12 m0;M �2 dx dx dx 2 dx dx 2 dx
cM1 cM2 ¼ cw12 exp 12
¼ cw12 G (13) (18)
gM1 gM2 RT 1 dm3 t1 t2 dmS
þ
2 dx 2 dx
where the last equality implicitly defines the factor G. Thus, Γ
includes all the deviations from an ideal behavior, but it is where we have used Eq. (12). Introducing d�=dx from Eq. (18)
rather hard to split it into activity coefficient and standard into Eq. (1) for the “bisulfate” and sulfate ions, their flux
chemical potential contributions; the mean activity coefficients densities are Eqs. (19) and (20):
of aqueous electrolytes are naturally determined and tabulated
� � � �
in a wide concentration range. Sorption experiments can be t2 k dm2 d� t2 k t3 dmS
j2 ¼ F ¼ t þ (19)
performed to determine membrane concentrations and, there- F2 dx dx F2 1 2 dx
fore, Γ. From Eqs. (7) and (13), the co-ion concentration is � �
(Eq. 14): t3 k dm3 d� t3 k dmS
j3 ¼ 2F ¼ ðt t2 Þ : (20)
4F2 dx dx 4F2 1 dx
sffi�
ffiffiffiffiffiffi�
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
X X 2
M
c ¼
2 þ þ G ðcw12 Þ2 : (14) Under steady-state conditions, the flux densities j2 and j3
2 2
vary with position due to the association reaction of cation and
sulfate to form “bisulfate”. On the contrary, the sulfate
For 2 : 1 and 1 : 2 electrolytes, cM2 is found as the solution of a constituent flux density is Eq. (21):
rd
3 order equation that is best solved numerically. In this work,
� �
Γ � 1 for the reasons discussed below. k 1 dmS
JS ¼ j 2 þ j 3 ¼ t 1 t 2 þ ðt 1 þ t 2 Þt 3 ¼
Sulfuric acid and sodium sulfate are electrolytes with three F2 4 dx
ionic species: X +, XSO4 , and SO42 labelled as 1 cation, 2 (21)
D2 D3 c2 c3 þ D1 D3 c1 c3 þ D1 D2 c1 c2 1 dmS
“bisulfate”, and 3 sulfate; here, X stands for H or Na, and D1 c1 þ D2 c2 þ 4D3 c3 RT dx
“bisulfate” denotes HSO4 or NaSO4 . The equilibrium condition
of the association reaction is m2 ¼ m1 þ m3 , which is equivalent does not vary with position. Eq. (21) can be transformed to
to Eq. (15) Eq. (17).
The ionic concentrations vary with position inside the IEM,
but the concentration gradients are relatively small in strongly

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charged membranes. Therefore, in order to obtain an analytical flux density JS across an IEM separating solutions with
expression of the diffusion coefficient DS of the electrolyte, it is concentrations cS ð0Þ and cS ðhÞ can be calculated.
reasonable to assume that K c is constant. By differentiating The calculations of the dissociation equilibria of NaSO4 and
Eq. (15) and the local electroneutrality condition; we have HSO4 with sulfate are described in Supporting Information. The
Eqs. (22) and (23): key finding is that the concentration-based dissociation con-
stant, Kc, is substantially higher that the thermodynamic
1 dc2 1 dc1 1 dc3 dissociation constant, Ka, and, hence, ignoring the activity
¼ þ (22)
c2 dx c1 dx c3 dx correction in the ionic equilibria would cause significant errors.

dc1 dc2 dc
¼ þ2 3 : (23)
dx dx dx Experimental Section

Combining Eqs. (22) and (23), the gradient of the chemical Materials
potential of the electrolyte, Eq. (16), is given by Eq. (24):
Sodium sulfate (Fluka, purity > 99.0 % (Germany)), sulfuric acid
(Merck KGaA with MQ 100 (Germany)), NaOH (Merck KGaA pellets
1 dmS 1 dmS dcS c1 þ c2 þ 4c3 dcS p.a. grade EMSURE® (Germany)), NaCl (Scharlau reagent grade ACS,
¼ ¼ (24)
RT dx RT dcS dx c2 c3 þ c1 c3 þ c1 c2 dx ISO, Reag. Ph Eur), and HCl 32 % (Merck KGaA p.a. grade EMSURE®
(Germany)) are used as received.
where cS ¼ c2 þ c3 is the stoichiometric electrolyte concentra- AR103P and CR61P from Suez Water Technologies and Solutions
tion. Thus, from Eqs. (21) and (24), the electrolyte diffusion are reinforced membranes composed of inert reinforcing fibers and
coefficient can be identified as Eq. (25): ion-exchange resins.[1] The chemical structures of their ion-
exchange polyelectrolytes are shown, in Ref. [38], Ref. [39]. The
properties listed in Table 1 include data from the manufacturer and
D2 D3 c2 c3 þ D1 D3 c1 c3 þ D1 D2 c1 c2 c1 þ c2 þ 4c3 calculated values. The water content WC of the hydrated ion-
DS ¼ ¼
D1 c1 þ D2 c2 þ 4D3 c3 c2 c3 þ c1 c3 þ c1 c2 exchange resin is the mass fraction of the water in the hydrated
D2 D3 D1 D3 D1 D2 (25) ion-exchange resin (not counting the inert reinforcing fibers),
c1 þ c2 þ c3 c1 þ c2 þ 4c3
1 1 1 : WC ¼ mw =mm (from the manufacturer). The water uptake of the dry
c1 þ þ c2 c3
D1 c1 þ D2 c2 þ 4D3 c3 ion-exchange resin is the ratio of the mass of sorbed water to the
mass of the dry ion-exchange resin,
WU ¼ mw =mdm ¼ WC=ð1 WCÞ. The volume fraction of water in
Although there is no simple, concentration-independent the hydrated ion-exchange resin is �w ¼ V w =V m ¼ WC1m =1w , where
expression for DS , Eq. (17) can be formally integrated between 1m is the density of the hydrated ion-exchange resin and 1w is the
the membrane boundaries as Eq. (26): density of water. The ion-exchange capacity ciex is the ratio of the
number of fixed-charge groups and the mass mdm of the dry ion-
Z cS ð0Þ exchange resin.
JS h ¼ DS dcwS (26)
cS ðhÞ We use a homogeneous membrane model, that is, the membrane
is considered as a homogeneous phase composed of ion-exchange
because JS does not vary with position. At x ¼ 0 the IEM is in resin, water and ions, with no pores or structural features. The
hydrophobic reinforcing fibers are not considered as part of the
equilibrium with an external feed solution with electrolyte
membrane as they are irrelevant for ionic transport. The membrane
concentration cS ð0Þ. At x ¼ h the IEM is in equilibrium with an fixed charge concentration [Eq. (27)]
external receiver solution with electrolyte concentration
cS ðhÞ � cS ð0Þ. For any position 0 � x � h, the local ionic ciex mdm ciex 1m c 1 ð1 WCÞ
concentrations inside the IEM can be considered to stay in cM ¼ ¼ ¼ iex m (27)
Vw ð1 þ WUÞ�w �w
equilibrium with a virtual external solution with electrolyte
concentration cwS , such that cS ð0Þ � cwS � cS ðhÞ. For every value is the number of fixed-charge groups per volume of sorbed water.
of cwS , the ionic concentrations inside an IEM with a concen- The values of cM shown in Table 1 have been calculated using
tration cM of fixed charge groups of charge number zM can be 1m � 1:0 g=mL and �w � 0:4. Alternatively,
evaluated as follows. First, we calculate the three local ionic �w ¼ WU=ðWU þ 1w =1dm Þ and 1=1m ¼ ð1 WCÞ=1dm þ WC=1w
could be used, with the density 1dm of the dry ion-exchange resin
concentrations cw1 , cw2 and cw3 in the virtual external solution
reported in Ref. [39].
(corresponding to position x) as the solution of three equations:
the definition cwS ¼ cw2 þ cw3 of the electrolyte concentration,
electroneutrality cw1 ¼ cw2 þ 2cw3 , and association equilibrium
�
K c cwS ¼ cw1 cw3 =cw2 . The local ionic concentrations inside the IEM
are cM1 ¼ cw1 e f , cM2 ¼ cw2 ef and cM3 ¼ cw3 e2f , where f ¼ f D�D can
be determined from the condition of local electroneutrality Table 1. Characteristics of the membranes.[1]
inside the IEM, zM cM þ cM1 ¼ cM2 þ 2cM3 . Thus, for every cwS , we can membrane area thickness WC WU ciex cM
evaluate cM1 , cM2 and cM3 and hence DS from Eq. (26). From the (type) [cm2] [mm] [meq/g] [M]
numerical evaluation of the integral in Eq. (26), the electrolyte AR103P (AEM) 10 570 0.39 0.639 2.37 3.6
CR61P (CEM) 10 580 0.44 0.786 2.20 3.1

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Diffusion Experiments
Diffusion experiments were carried out in a two-compartment cell
setup with a single IEM separating them. The electrodialysis cell
(Micro Flow Cell, Electrocell, Denmark) is assembled with IEMs, two
leak-free reference electrodes (LF-1, 1 mm OD, Ag/AgCl from
Alvatek, United Kingdom), as well as Pt coated Ti anode and
cathode (Figure 1). The active membrane and electrode area are
10 cm2 and the membrane spacing is 3 mm. The flow rate was
100 mL/min for each liquid channel (width 3 mm) and was
controlled by peristaltic pumps (Watson Marlow 323). The feed
compartment concentration was 0.25 M and the receive compart-
ment concentration was 0.01 M. The membrane was immersed in
0.25 M electrolyte first for 24 h. Electrolyte diffusion was monitored
by measuring the conductivity of both compartments with WTW
TetraCon 925 conductometer. Conductivities were then converted Figure 2. Schematic representation of membrane resistance measurement.
to concentrations with the data from the CRC Handbook of
Chemistry and Physics.[40] The concentration of feed and products
were also verified by titration with Titrette® 25 mL class A precision.
Scanning Electron Microscopy (SEM)
Resistance Measurements The membranes were imaged using a scanning electron micro-
scope Tescan Mira3. A high voltage of 2–5 kV was applied to the
A variable number N (from 1 to 4) of membranes (IEM*) was placed specimen. In this study, a low-vacuum mode was used with the
between two auxiliary IEMs (Figure 2). The distance between two backscattering of electrons. The sputtering of membrane surface
reference electrodes was 1.7 mm with one membrane and changed was also carried out using Quorum Q150T ES before SEM. The
accordingly by the number of membranes. All membranes were purpose of sputtering was to increase the surface conductivity of
equilibrated with the electrolytes (0.15 M) for 24 h prior to the the membranes. In general, the non-conductive surface acts as an
measurements. Spacers were placed in the compartments to cause electron trap, which results in the accumulation of electrons on the
turbulence close to the membrane surface. The total electrical surface is called “charging” .[41] The conductive coated material acts
resistance [Eq. (28)] as a path that allows the charging electrons to be removed from
the membrane surface. The charging electrons cause extra-white
RTOT ¼ NRM þ Raux (28) regions on the sample, which can influence the image information
and quality. Au Pd was used as a conductive material layer. Pure
of the cell was measured in 0.15 M HCl, NaOH, NaCl, H2SO4, and argon was used as a backfill process gas.
Na2SO4 using EIS, as the intercept on the real axis of the Nyquist The AR103P and CR61P membranes are identical in most aspects,
plot. The auxiliary resistance Raux consists of the electrode and such as thickness, color, and chemical stability. The orthogonal
solution resistances. The resistance RM of a single membrane (IEM*) cross-section images (Figures 3a and 3c) depict the ion-exchange
was obtained by fitting the RTOT vs. N measurements to Eq. (28). resin between the supporting polymer reinforcing fiber web
Due to the imperfectly smooth surface of the membranes, RM may (diameter 20 μm). This morphology becomes highly conductive
contain a small contribution associated to the solution layer when immersed in an electrolyte. Furthermore, free leakage of
between membranes. The impedance measurements were carried electrolytes is not possible due to their tightly packed structure.
out with an AUTOLAB PGSTAT128 N potentiostat and Nova 2.1 The visible surface cracks are due to drying of both membranes
software. The impedance spectra were measured at the open circuit (Figures 3b and 3d) before SEM imaging.
potential with an AC amplitude of 10 mV and a frequency range
from 10 kHz to 0.5 Hz.

Figure 1. ElectroCell used for diffusion experiments.

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Figure 3. Cross-section (a) and surface (b) SEM images of AR103P. Cross-section (c) and surface (d) SEM images of CR61P.

Result and Discussion of sulfate (or bisulfate) in a CEM is lower than that of OH or
Cl . Similar results were reached by Kiyono et al.[42] and Wycisk
Figure 4 shows the concentration changes in the receiver et al..[43] Comparison of NaCl and HCl fluxes also makes sense
compartments during diffusion experiments. As anticipated, because of the higher mobility of protons.
acids (HCl, H2SO4) diffuse in an AEM significantly faster than In the AEM, on the contrary, NaOH appears to diffuse the
salts (NaCl, Na2SO4), because of the high mobility of proton. most slowly, even more slowly than Na2SO4. From the Donnan
Furthermore, sulfuric acid shows an exponential concentration equilibrium calculations, the concentration difference across the
rise, while the concentrations of the other electrolytes are AEM was found to be for Na2SO4 ca. 5-fold to that of NaOH. The
changing more gradually, almost in a linear fashion. The ultimate reason for this is the Donnan equilibrium that was on
observed diffusion rate in AEM is H2SO4 > HCl > NaCl > Na2SO4 > the feed side was ca. 25 mV for Na2SO4 and ca. 70 mV for NaOH,
NaOH, whereas for CEM it is NaOH > HCl > NaCl > Na2SO4 � because the Donnan potential is lower when the counterion is
H2SO4. From this trend, the membrane conductivity behavior is divalent. The higher the Donnan potential is, the more it
also predicted. equalizes concentration differences across the membrane.
An interesting and perhaps a bit surprising observation is Hence, when analyzing flux data, looking at the diffusion rates
that, in the CEM, the flux of NaOH is twice as high as that of only does not suffice, but the chemistry behind them must be
NaCl and much higher than that of H2SO4, underlining the fact understood as well.
that the co-ion defines mainly the rate of diffusion. The mobility

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Figure 4. Receive compartment concentration in diffusion experiments a) CEM, b) AEM. [system = Feed (0.25 M) j Membrane j Receive (0.01 M)]

Figure 5. Resistances of cells with stacked IEMs and various electrolytes.

The electrolyte flux density is determined from the mass The resistance between the reference electrodes in different
balance as Equation (29): electrolytes is plotted against the number of membranes (IEM*)
in Figure 5. The dependence is linear, as expected. The auxiliary
� �
V dc resistance is obtained from the intercept of the plots. Because
J12 ¼ (29)
A dt t¼0 of the relatively higher mobility of proton and hydroxide, the
membrane conductivity is noticeably higher when the electro-
where V is the volume of the feed or the receiver compartment lyte is an acid or base (NaOH, HCl, H2SO4) than when it is salt
and A is the geometrical area of the membrane. The term (NaCl, Na2SO4, Figure 6).
ðdc=dtÞt¼0 is the initial slope of the concentration vs. time curve. From the results of the diffusion experiments and the
The initial slope was determined by fitting the receiver electrical resistance RM measurements, JM12 and kM ¼ h=ARM are
compartment concentration to an exponential function of time determined. Inserting these values in Eqs. (9) and (10), we have
and calculating its derivative at t = 0. This is done because the a system of two equations that can be numerically solved to
concentration in the receiver (feed) compartment increases obtain the two unknowns1, DMþ and DM , e.g., using Mathema-
(decreases) in an exponential manner. Also, when comparing tica®. The diffusion coefficient of co-ions is higher than that of
measurements with COMSOL simulations where concentrations counterions with the exception of H + in the CEM, which is not
were fixed at the limits of the simulation domain, the initial flux
is needed. 1
Here we use, for the case of clarity, symbols D + and D because cations are
counter-ions in the CEM but co-ions in the AEM, and anions vice versa.

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Table 3. The ionic diffusion coefficients [10 7 cm2 s 1] of weak electrolytes:

subscript 1 refers to H + or Na +, 2 to HSO4 or NaSO4 , and 3 to SO42 .
Notation similar to Table 2.
CEM, cM = 3.1 M AEM, cM = 3.6 M
electrolyte DM1 [a]
DM2 DM3 DM1 [b]
DM2 DM3

Na2SO4 4.11 5.60 4.30 1.21 1.21 1.32

(3.1) (4.3) (4.3) (0.9) (0.9) (1.3)
H2SO4 13.2 5.42 4.17 56.8 7.94 1.19
(1.4) (4.17) (4.17) (6.1) (6.1) (1.9)

[a] DM2 =Dw2 ¼ DM3 =Dw3 *, [b] DM1 =Dw1 ¼ DM2 =Dw2 .

but three diffusion coefficients, an extra assumption, as

Figure 6. Conductivities of the IEMs in the studied electrolytes (0.15 M). indicated in the Table 3, is needed to solve the problem.
Solving the ternary case equation (26) numerically is quite
tedious and demanding. Using COMSOL Multiphysics it can be
surprising because of its high mobility. Also, it is commonly avoided because a user does not need to solve any equations
observed that proton leakage through AEMs is quite high, as or write a computing script, but choosing an appropriate model
we observed in our previous paper.[35] Also, the higher mobility from a menu, in this case the Nernst-Planck equation with
of OH seems to agree with its leakage through the CEM.[35] electroneutrality, suffices. Naturally, fundamental understanding
In the CEM, the diffusion coefficients of the counterion are of physics and chemistry is required to set-up a meaningful
ca. 3–4 % of their aqueous values at infinite dilution, while in model. We described these calculations in detail in our previous
the AEM it is only of the order of 1–2 % because of the higher paper.[35] Briefly: Ternary Current Distribution module was
fixed charge density (Figure 7). The diffusion coefficients of the applied with the Donnan boundary conditions at the solution-
co-ions are 7–9 % and 4–16 % of their aqueous values at infinite membrane interfaces; the sulfate dissociation equilibria were
dilution in the CEM and AEM, respectively (Table 2). It has to be incorporated as a reaction term in the steady-state transport
emphasized that the values are averaged over the sorbed water equations; at the limits of the simulation domain the concen-
volume and, thus, do not provide values for the condensed trations of the species were fixed; at one limit the Galvani
phase and free counter-ions separately. potential was set to zero and at another limit electric current
The procedure for the determination of the diffusion was set to zero, hence ensuring pure diffusion.
coefficients of the ionic species in Na2SO4 and H2SO4 is Simulations of the conductivity measurement, keeping the
explained in the Theoretical section. Because there are two solution concentrations equal on both sides of the membrane,
experimental quantities, the diffusion flux and the conductivity, showed that in the case of H2SO4 and the CEM, the only
meaningful species in the membrane is H +. Therefore, from the

Figure 7. Comparison of ionic diffusion coefficients in a) CEM, b) AEM in different strong electrolytes.

6
Table 2. Ionic diffusion coefficients [10 cm2 s 7] of strong electrolytes in IEMs. In parenthesis the values relative to the aqueous value at infinite dilution,
[%].
CEM, cM = 3.1 M AEM, cM = 3.6 M
electrolyte DMþ DM DMþ DM

NaCl 0.44 (3.4) 1.40 (7.0) 1.23 (9.5) 0.35 (1.7)

NaOH 0.60 (4.6) 4.57 (8.8) 0.56 (4.3) 0.37 (0.7)
HCl 2.51 (2.7) 1.86 (9.3) 15.6 (16.7) 0.34 (1.7)

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measured conductivity the diffusion coefficient of H + was absence of electric current a diffusion potential is developed
readily found (Table 3). This value was then used to simulate across the IEM. Thus, the electrolyte flux density, when written
the diffusion experiment, keeping the ratio D2/D3 the same in in terms of ionic flux densities, consists of diffusional and
the solution and membrane phases. In the case of Na2SO4 and migration contributions. For the case of sulfuric acid, the
the CEM, the conductivity is determined by Na + because the contributions [Eqs. (30) and (31)]
concentrations of the sulfate species are very low, ca. 2.0 mM
only. Hence, DM1 was readily found and keeping again the ratio dc2 dc3
JS;dif ¼ j2;dif þ j3;dif ¼ D2 D3 (30)
D2/D3 constant they were found from the diffusion flux. dx dx
In the case of Na2SO4 and AEM, sulfate determines the
conductivity almost entirely (98 %) which leads to the value of d�
JS;mig ¼ j2;mig þ j3;mig ¼ ðD2 c2 þ 2D3 c3 ÞF (31)
DM3 , and applying the constraint as indicated the other diffusion dx
coefficients were found. The most tedious case was H2SO4 with
the AEM, because all the ions have non-negligible contributions are shown in Figure 8. The migration contribution is actually
to the conductivity. The ionic diffusion coefficient values that higher than the diffusional one.
showed agreement between the measured electrolyte diffusion Finally, it must be realized that a concentration difference
flux density and that calculated with Eq. (26), using a Mathema- across an IEM creates an osmotic pressure difference that
tica script, were inserted in the COMSOL model, and an causes water flow in the opposite direction of the diffusion flux.
agreement within the accuracy of the measurements (ca. 5 %) In our previous paper,[35] we measured the volume change due
were reached. The high mobility of proton, causing leakage to electroosmosis at varying current densities. The volume
across AEMs is again seen in its diffusion coefficient that stands changes were 1–20 mL in 2 h. If we extrapolate this data to zero
out from Table 3. current density, a definite value cannot be given but it appears
It has to realized that the values given in Table 3 are very to be very small. Therefore, osmosis was ignored in the current
good estimates, not absolute ones. Previously,[35] we assumed study.
that the diffusion coefficient values were 10 % of their aqueous In Eq. (13) the parameter Γ, including all the deviations from
values at infinite dilution, except for proton 60 %. In that work ideal behavior, was introduced. As can be seen, it contains both
the diffusion coefficients were corrected for the free volume the activity coefficient corrections and the standard chemical
(40 %) and the tortuosity (1.5) of the membrane which makes a potential difference. Kamcev et al.[36] assumed that the standard
coefficient 3.75, i. e. 10 % becomes ca. 2.7 % and 16 % for proton. chemical potentials were equal in the aqueous and membrane
Hence, we can conclude that the assumption was quite phases and that Eq. (32)
appropriate considering that with electric current the main
�
transport mechanism is migration. Looking at Eq. (2) it is gw� 2
G¼ (32)
obvious that when all diffusion coefficients are scaled with the gM1 gM2
same number, the transport number does not change at all.
One of the advantages of COMSOL simulations is that it is can be calculated from electrostatics using Manning’s conden-
possible to look at the components of the flux density sation theory. Calculating the denominator in Eq. (32) requires
separately, which would be very hard in an analytical solution the parameter ξ = λΒ/b, the ratio of the Bjerrum length, λB, and
or when writing a computing script. For any electrolyte with the average distance between the fixed charge groups, b. The
different diffusion coefficients of counterions and co-ions, in the parameter b would probably vary around 10 Å, and the Bjerrum

Figure 8. a) Diffusion and migration contributions of the sulfate constituent flux in the AEM. b) Potential profile across the AEM.

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length depends on the relative permittivity inside the mem- Solutions is acknowledged for the supply of the membranes. Mr.
brane pores. Hence, Γ would vary significantly on the choice of Heikki Pajari (Sr. Scientist at VTT Technical Research Centre of
these parameters. The theory applies to strong binary electro- Finland Ltd) is acknowledged for commenting on the manuscript.
lytes, not to our cases with Na2SO4 and H2SO4. Also, the J.A.M acknowledges the funding from project PID2021-126109-
deviations from ideal behavior are not only electrostatic in NB I00, Ministry of Science and Innovation(Spain), and FEDER.
nature and they should include specific interactions between
an ion and a membrane. In aqueous solutions the standard
chemical potential μ0 reflects the hydration energy of an ion, Conflict of Interest
which also depends on the relative permittivity of the medium.
Therefore, due to the uncertainty of its accurate value, we are The authors declare no conflict of interest.
not accounting for the effect of Γ. Its effect on the concen-
tration gradient in the membrane or its conductivity would not
be any larger than the inherent uncertainty of the experimental Data Availability Statement
data.
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
Conclusions
Keywords: ionic transport · ionic diffusion · ion-exchange
The diffusion of various ions across the IEMs is studied and membranes · COMSOL Multiphysics · diffusion coefficients
diffusion coefficient values of different electrolytes are exper-
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