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org/IECR Article

Comparison of Models for the Prediction of the Electrical

Conductivity of Electrolyte Solutions
Saman Naseri Boroujeni, Xiaodong Liang, Bjørn Maribo-Mogensen, and Georgios M. Kontogeorgis*
Cite This: Ind. Eng. Chem. Res. 2022, 61, 3168−3185 Read Online

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ABSTRACT: It has been almost one century since Onsager developed the limiting law of
equivalent conductivity of electrolyte solutions. Thenceforth, many models have been
developed; however, they have not been assessed thoroughly and systematically. This paper
comprehensively investigates the accuracy and reliability of six equivalent conductivity
models, namely, the Debye−Hückel−Onsager limiting law (DHOLL), extended law
(DHOEE), smaller ion shell (DHOSiS), along with the simplified and full mean spherical
approximation (MSA, MSA-Simple), and Quint−Viallard (QV). To this aim, we have
prepared a database of experimental data for 126 electrolytes. The accuracy of the models is
examined with the help of graphical methods and error analysis over a wide range of
concentrations ([0, 18] mol/L) and temperatures ([0, 100] °C). Moreover, the origin of
possible errors of models is inspected with a term-by-term analysis of relaxation and
electrophoretic effects. It is shown that the absolute average deviation of models depends
highly on the electrolyte type, and it is generally smaller for 1:1 salts, especially at low
concentrations (less than 5%). The error evolution with concentration also reveals that MSA-Simple and DHOEE are more reliable
over a wide range of concentration and electrolyte types. It is concluded that MSA-Simple predicts the equivalent conductivity at
lower temperatures and the trend of Λ versus T more satisfactorily than the other models.

1. INTRODUCTION Similarly, Pitts,19 Fuoss-Justice,2,20 and Fuoss−Hsia/Fernán-

Equivalent conductivity (EC) always has been of great
significance for scientists and engineers. However, it has never
been as essential as it is today. For instance, the optimization of
energy storage devices (batteries, fuel cells, etc.)1 depends on
equivalent conductivity as the primary transport property. As it
is not practically and economically feasible to measure
equivalent conductivity experimentally over a wide range of
concentrations and temperatures (screening of thousands of
systems), predictive methods are of the essence in aiding the
better digital design of these devices. In addition, since the
equivalent conductivity can be measured precisely even at low
concentrations (LC) compared to other thermodynamic and
transport properties of electrolyte solutions,2 the data coupled
with predictive models are routinely used to indirectly estimate
other thermodynamic properties such as association con-
stants.3−6 As a result, an accurate and reliable model is desirable
to predict the conductivity of an electrolyte solution with
accepted accuracy.
Lars Onsager (Chemistry Nobel Prize winner 1968)7,8 was
the first to develop a correct version of the limiting law (Debye−
Hü ckel−Onsager limiting law (DHOLL)) of equivalent
conductivity by improving the theory of Debye and Hückel.9
After that, in a series of papers, Fuoss and Onsager (FO)10−18
tried to improve the DHOLL for finite ion size, ion−ion
association and considered higher terms of Onsager’s continuity
equation. However, their models are limited to symmetrical and
single-salt systems.
dez-Prini21−23 models have been developed only for sym-
metrical electrolytes. They have a similar mathematical form to
eq 1; however, as mentioned by Barthel et al.,3 from the
derivation point of view, they differ in the form of the pair
distribution function, boundary conditions, the approximation
of relaxation, and electrophoretic terms, and consideration of
additional factors.
Λ = Λ0 − Sc 0.5 + Ec ln(c) + J1c + J2 c1.5
(1)
In addition, these forms of EC models have been used mainly for
the analysis of EC data for associated electrolytes by fitting J1, J2,
Λ0, and KA. However, J1, and J2 can be calculated by analytic
equations (see the Appendix of ref 24).
In 1978, Quint and Viallard24−26 and Lee and Wheaton27−29
generalized the model presented by Fuoss and Onsager8 and
Fuoss,30 respectively, for unsymmetrical multisalt solutions.
However, the formulation for multisalt systems is very complex
and difficult to apply in practice. The main drawback of the
mentioned models is that the same ion size has been assumed in
Received: November 4, 2021
Revised: February 2, 2022
Accepted: February 2, 2022
Published: February 18, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.iecr.1c04365

3168 Ind. Eng. Chem. Res. 2022, 61, 3168−3185
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Table 1. Summary of the Mathematical Formulations of Conductivity Models

model relaxation term electrophoretic term
ΔX |ZiZj| e 2q Δυi F2
DHOLL = − 12πε ε k T 1 + q κ =− |Zi|κ
X 0 r B υi0 6πηNAλi0
2 2
ΔX ZiZje q κ ZiZje q κ Δυi F2 κ
DHOEE
X
= 12πε0εrkBT 1 − q (1 + κa)κa
[e κa(1 − q ) − 1] ≅ 12πε0εrkBT 1 + q 1 + κa υi0
=−
6πηNAλi0
|Zi| 1 + κa

|ZiZj| e 2 Δυi F2
DHOSiS ( ΔXX )i = 12πε ε k T 1 P+* qq ω†Ψ*i
0 r B υi0
=
6πηNAλi0
|Zi|ω†Ψ*i

ΔX −1 κq2e 2 |ZiZj| (1 − e−2κqd) Δυi kBT Γ

MSA-Simple = . =−
X 24πε0εrkBT d(1 + Γd)2 [κq2 + 2Γκq + 2Γ 2(1 − e−κqd)] υi0 3πηDi0 1 + Γd

ΔX1Rel ΔX2Rel
Hyd Δυi Δυi1 Δυi 2
MSAa ΔX
= + +
ΔX1
, eqs S1, S10, and S17 = + , eqs S18 and S19
X X X X υi0 υi0 υi0
ΔX1,2 ΔX2P Δυi
QVa ΔX
= + , eqs S20 and S21 υi0
, eq S22
X X X
a
The mathematical formulation is presented in the Supporting Information.

them. Bernard et al.31 developed an EC model assuming
different ion sizes in the framework of MSA. After that, Anderko
et al.32 and Turq et al.5 have improved the MSA model,
respectively, for multisalt systems and associated electrolytes.
Chhih et al.33 also simplified the MSA model for practical use by
ignoring the relaxation and electrophoretic terms higher than 1.
Recently, Fraenkel34 has developed a new model based on the
“Smaller ion Shell” theory and the DHOLL known as DHOSiS.
Similar to the MSA model, DHOSiS considers the differences
between the cation and anion size. On the other hand, the
concentration range of applicability declared by the author
(0.101 mol/L for KCl) is narrower than the MSA model (1 mol/
L for KCl).
There are a few studies that compare the performance of the
EC of the electrolyte solutions. Bianchi et al.35 compared
MSA5,31 and simplified MSA33 models with the Fuoss−Hsia/
Fernández-Prini21−23 and Lee and Wheaton27−29 for sym-
metrical and asymmetrical electrolyte solutions at very low
concentrations. De Diego et al.36 conducted an investigation on
the EC models derived from the Falkenhagen37 theoretical
model for dilute solutions. Although they studied various 1:1
and relaxation terms of the models to better understand their
differences and appreciate their behaviors.
The manuscript is structured as follows. First, in Section 2, the
EC modes are briefly described, and their mathematical
formulations and parameters are presented. Then, a summary
of the experimental database is outlined. After that, the results
are presented as graphical comparisons, error analysis, and term-
by-term investigation in Section 3. Finally, in Section 4, we
present our conclusions.
2. MODELS FOR EQUIVALENT CONDUCTIVITY
In this work, we have considered six important EC models:
DHOLL, Debye−Hü c kel−Onsager extended equation
(DHOEE), DHOSiS, MSA (simple and full versions), and
Quint−Viallard (QV). Although the origin of these models is
almost the same, the final forms are quite different due to
different assumptions or different pair distribution functions.
Besides the derivation, these models have been presented by
their authors in different ways. Here, we present all of the models
in a unified way to facilitate the comparison between models. As
a result, the general form of the EC models can be written as

ij Δυ yzi
shown in eq 2.
ΔX zy
electrolytes up to very high concentrations (HC), the employed

λi = λi0jjj1 + 0i zzzjjj1 + zz
EC models are empirical rather than theoretical. In addition,
j zk X {
k i {
Barthel et al.3 analyzed a few EC models of the form of eq 1 for
associative electrolytes such as (i-Pent)3BuNI in ethanol and υ (2)
compared the association constants derived from six EC models
This equation is based on the interpretation of Debye and
(Table 3.10 in ref 3) at low concentrations. However, they did
Hückel. They attributed the mobility reduction of ions with
not compare the performance of these models.
concentration under an external electric field to relaxation and
Unfortunately, even though many models have been
developed for the EC, which model(s) perform(s) best is not electrophoretic effects. ( ΔXX ) is the reduction of mobility due to
clear, at least for a wide range of systems and conditions.
Furthermore, their application range, accuracy, and reliability
are limited to results presented mostly by the developers. As a
relaxation, and( ) is the reduction due to electrophoretic
Δυi
υi0

effects. Note that the term ( × )λ is ignored for the

Δυi ΔX 0
result, a systematic analysis of these models for different υi0 X i
electrolytes and over a wide range of concentrations and DHOLL, DHOEE, DHOSiS, and QV models. Thus, for these
temperatures is useful.

ij ΔX yzz
models, the general form is eq 3.

λi = λi0jjj1 + 0i +
In this work, the target is to evaluate the predictive ability of
zz
j X z{
six known EC models at an ample range of concentrations and Δυ
k
temperatures. Moreover, we focus on aqueous solutions of υi (3)
different electrolytes (1:1, 1:2, 1:3, 1:4, 2:1, 2:2, 2:3, 2:4, 3:1, and
3:2) in a low-pressure conditions. We analyze the accuracy and Table 1 presents the relaxation and electrophoretic terms of all
reliability of the models with the help of experimental data for models considered, and then we discuss each model separately.
126 electrolytes. We compare the models’ predictions with In the context of the electrical conductivity of electrolyte
experimental data up to high concentrations and temperatures. solutions, four properties, namely, specific conductivity, molar
We also evaluate the models’ accuracy with the help of error conductivity, equivalent conductivity, and ionic conductivity,
analysis. Finally, we individually examine the electrophoretic are used. To clarify the difference between them and avoid
3169 https://doi.org/10.1021/acs.iecr.1c04365
Ind. Eng. Chem. Res. 2022, 61, 3168−3185
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Table 2. Electrical Conductivity-Related Properties

properties formula explanation
l
specific conductivity (σ) σ = GA conductance of a cube of solution (geometry normalization)
σ
molar conductivity (Λ) Λ= c
specific conductivity of 1 mol/L of solution (concentration normalization)

equivalent conductivity Λ ( 1
M A )=
νi |Zi| ν+ ν−
1 σ
νi |Zi| c
=
Λ
νi |Zi|
, i = + or − specific conductivity of 1 equiv g of solute (charge normalization)

ionic conductivity (λi) σ = ∑i =+, − νi|Zi|cλi contribution of ions of the same kind to the equivalent conductivity
Λ = ∑i =+, − νi|Zi|λi

Λ ( 1
M A )=∑
νi |Zi| ν+ ν−
λ
i =+, − i ( 1
|Zi|
M Zi )
misunderstanding, we explain their differences and their an identical diameter (distance of the closest approach). Also,
relations. Table 2 summarizes the connection between them
for the relaxation field, the exponential part has been
and their physical meaning.
IUPAC does not suggest the use of the word “equivalent approximated with the first-order Taylor series, and the
conductivity” anymore due to ambiguity. It recommends the use higher-order terms of κa have been ignored. Consequently,
of molar conductivity of 1 mol/L of salt MZ+AZ− with the
νi |Zi| the ionic conductivity and EC of this model can be written as eqs
( 1
M Z+AZ− ) instead of equivalent conductivity. 38

ÄÅ ÉÑ
symbol of Λ 7 and 8, respectively.

ÅÅ ÑÑ
νi |Zi|

Å Ñ κ
λi = λi0 − ÅÅÅÅ λi0 ÑÑÑÑ
For example, instead of the equivalent conductivity of MgSO4, 2

ÅÅ 6πηNA 12πε0εrkBT 1 + q ÑÑ 1 + κa
the molar conductivity of 1/2 mol/L of MgSO4 with the symbol F 2 | Z Z | e q

ÅÇ ÑÖ
i j
of Λ(1/2 MgSO4) can be used. |Zi| +
In this study, we have presented the conductivity models with
the equivalent conductivity with symbols Λ and λi in which the (7)

ÄÅ ÉÑ
ÅÅ ÑÑ
ÅÅ F 2 0Ñ
( 1
) and ( 1
) are omitted, respectively, for
Λ ÑÑÑÑ
terms M A M Zi
Λ = Λ − ÅÅÅ
νi |Zi| ν+ ν− |Zi|
|ZiZj|e 2
ÅÅ 6πηNA 12πε0εrkBT 1 + q ÑÑ
q

ÅÇ ÑÖ
the sake of simplicity. On the other hand, the molar 0
(|Zi| + |Zj|) +
conductivities are presented in Section 3.
2.1. Debye−Hückel−Onsager Limiting Law (DHOLL). κ
This model was developed by Debye and Hückel9 and then (8)
1 + κa
improved by Onsager.39 It is the most basic model for the
prediction of the EC. They developed the model by ignoring the
size of the ions and assuming that the relaxation field is much 2.3. Debye−Hückel−Onsager Smaller Ion Shell (DHO-
smaller than the electric field (ΔX ≪ X). Furthermore, for the SiS). The DHOSiS model has been recently proposed by
electrophoretic term, the higher terms beyond the first one have
Fraenkel34 to improve the DHOLL using the so-called “smaller
been omitted. Then, after some algebra, they could show that the
EC of electrolyte solutions is linearly dependent on the square ion shell” (SiS) theory. He has made three main changes to the
root of concentration at infinite dilution. Finally, the DHOLL
DHOLL; first, he multiplied the ω value of DHOLL to make it

ÅÄÅ ÑÉÑ
can be written in the format of eq 4 to eq 6
ÅÅ F 2 0Ñ
Ñ
Å λi ÑÑÑÑκ
practical for multivalent electrolytes. Second, he considered the
λi = λi − ÅÅÅ
|ZiZj|e 2
ÅÅ 6πηNA 12πε0εrkBT 1 + q ÑÑ
q

ÅÇ ÑÖ
0 differences between cation and anion sizes and thus adopted an
|Zi| +
(4) unrestricted primitive model (UPM) approach. Third, he

ÅÄÅ 2 ÑÉ
multiplied an oversize offset factor to resolve the over-

q Λ0 ÑÑÑÑ
Λ = λi + λj
ÅÅ F (|Zi| + |Zj|)
= Λ − ÅÅÅ Å ÑÑκ
compensation of the second change. The model equations are

12πε0εrkBT 1 + q ÑÑÑ
|ZiZj|e 2
ÅÅ
ÅÇ ÑÖ ÄÅ ÉÑ
0 shown in eqs 9−13.
+

ÅÅ ÑÑ
6πηNA
Å Ñ
λi = λi0 + ÅÅÅÅ λi0 ÑÑÑÑω†Ψ*i
2

ÅÅ 6πηNA 12πε0εrkBT 1 + q ÑÑ
(5) F 2 | Z Z | e P *q

ÅÇ ÑÖ
i j
|Zi| +
|ZiZj| λi0 + λj0
q= (9)
|Zi| + |Zj| |Zi|λj0 + |Zj|λi0
ÄÅ
(6)

ÅÅ
Å F2
Λ = Λ − ÅÅÅÅ
2.2. Debye−Hü ckel−Onsager Extended Equation |ZiZj|e 2
ÅÅ 6πηNA i =+, −
P*q
ÅÇ
(DHOEE). The DHOEE is the equivalent model in the 0
∑ |Zi|Ψ*i +
ÉÑ
12πε ε k T 1 + q
ÑÑ
conductivity models to the extended Debye−Hückel equation 0 r B

∑ λi0Ψ*i ÑÑÑÑÑω†
for the activity coefficient models. Its relaxation term has been

ÑÑ
derived by Falkenhagen et al.37 using the Eigen−Wicke
ÑÖ
distribution function.41 Moreover, a finite ion size has been
i =+, − (10)
considered in this model and all ions have been assumed to have
3170 https://doi.org/10.1021/acs.iecr.1c04365
Ind. Eng. Chem. Res. 2022, 61, 3168−3185
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Table 3. Parameters and Properties Needed for Each Model (Green Tick: Ion-Specific, Black Tick: Salt-Specific)a

a
It can be calculated from equivalent conductivity at infinite dilution (ECID).

l |Z |
o
o
o
o
o
o υ− +
Moreover, there are some minor modifications for the MSA
o
|Z+| 0
o
− 0

P* = m
t + t − for |Z+| ≤ |Z −| model primarily because of simplifying its implementation.
o
o
υ+
o
o
Some authors tried to present an explicit formulation for the
o
o
o
screening length parameter.42 Some other authors dropped
o
|Z −| 0 |Z+| 0
n υ+
t+ + t − for |Z+| ≥ |Z −|
υ− some expressions in the formulation (Γ 2d 2 in eqs S12 and S15)

l |
2[e κ(a − b+) − 1] − κ(a − b+) o
−κ o
due to the lack of numerical importance.32 The computational
o o
m1 }
1 + κa o o o
o
effort of solving the implicit screening length equation is not

n ~
Ψ*+ = − problematic if a proper method is used. However, the MSA
1 + κb+ model cannot predict the EC at high concentrations for some
electrolytes (e.g., LaCl3) in water without the second

−κ l 2[e κ(b−− a) − 1] − 2κ(b− − a) |

(11)

o
o o
o
modification.
m
o }
o
o o
In this work, we have used the original formulation31 for two
1 + κa n ~
Ψ*− = 1 + reasons. First, in this work, we have tried to conduct a fair
1 + b−
comparison. Thus, comparing a modified version of a model
b+ = 2r+ , b− = 2r − , a = r − + r+ with an original version of another model is not fair. Second,
(12)
dropping an expression because it has a minor effect on the
results at low to medium concentrations (MC) is not a strong
(λ+0 − λ−0)2 justification. Consequently, in this work, the results of MSA are
ω† = 1 + P*qκa from the original formulation.
3λ+0λ−0 (13) The MSA-Simple model33 is the restricted primitive model
The derivation procedure of the DHOSiS model is not entirely (RPM) version of the MSA that only considers the original
clear, but it can be seen that Fraenkel did not follow the method model’s first approximation for the relaxation and electro-
used by other authors. The derivation procedure of all models phoretic terms. The mathematical formulation of this model has
(except the DHOSiS) presented in this paper is by solving the been written in eqs 14−18.
Onsager continuity equation8 (or the Ebeling generalized κq2e 2|ZiZj|
form40) for the relaxation term. The output of this mathemati- ΔX 1
=−
cally demanding problem for all models is a salt-specific X 24πε0εrkBT d(1 + Γd)2
relaxation term. However, the relaxation term of DHOSiS is (1 − e−2κqd)
ion-specific.
2.4. Mean Spherical Approximation-Based Models [κq2 + 2Γκq + 2Γ 2(1 − e−κqd)] (14)
(MSA Model). This model is derived from the generalized
derivation procedure of Ebeling et al.40 and the MSA correlation Δυi kBT Γ
=−
function3 for the equilibrium part. Additionally, Bernard et al.31 υi 0
3πηDi0 1 + Γd (15)
have used Poisson’s equation for the perturbation part of the
total potential. To solve the inhomogeneous continuity κ
2Γ =
equation, they have used Green’s function techniques. The (1 + Γd) (16)
significant point of this model is that it is an unrestricted
primitive model, and an ion-specific size parameter has been 2 0 2 0
e 2 ρi Zi Di + ρj Zj Dj
introduced in the formulation (crystallographic ion size). In this κq2 = γ 2 =
work, we consider two versions of MSA-based EC models: the ε0εrkBT Di0 + Dj0 (17)
original version31 and the simple version.33 The mathematical
formulation of the original model is quite complex and lengthy, ∑i ρi Zi2di
and the reader can refer to the original paper31 or the Supporting d=
Information. ∑i ρi Zi2 (18)

3171 https://doi.org/10.1021/acs.iecr.1c04365
Ind. Eng. Chem. Res. 2022, 61, 3168−3185
Industrial & Engineering Chemistry Research
Table 4. Parameters and Range of Applicability of the Water Viscosity Correlation47
T0: 293.15 K T: 273.15−373.15 K
a1 a2
−2.453949 × 10−2 1.854797 × 10−4
This model has an advantage over other RPM models in that an
equation has been suggested for the salt-specific size parameter
(eq 18). This function reduces to d = 1/2∑idi for symmetrical
electrolytes. For asymmetrical electrolytes, however, it gives
more weight to the ion with a higher valence type. Furthermore,
Blum42 first derived this equation by solving the implicit
equation of the MSA screening parameter at the limit zero
( lim Γ(ρi , di , Zi , T , εr)).
Γ→ 0
2.5. Quint and Viallard Model (QV). This model is an
improvement to the models developed by Fuoss and Onsager
(FO),8,11−18,30 in a way that higher-order terms of the relaxation
and electrophoretic have been considered. Additionally, unlike
the FO models, the QV model24−26 is applicable to multisalt
systems and unsymmetrical electrolytes. In the original paper,
the authors have written the final formulation of the model as
shown in eq 19
λi = λi0 − SimI 0.5 + Ei′ mI ln(I ) + J1mi I − J2mi I1.5 + O(I 2)
In this equation, E′i ,
Smi , m
Jm1i, Jm2i
and are complex functions of
ionic conductivity at infinite dilution (ICID), ionic strength, the
distance of closest approach, universal constants, and ions
valence type.
In the formulation of eq 19, an expression with dimension
appeared in the logarithm, making the model’s programming
without knowing the units very tricky. In this work, we have
reconsidered the QV model using the formulation of relaxation
and electrophoretic terms (eqs S20−S24) individually and then
combined them into eq 3.
2.6. Parameters and Properties Used in the Models. As
shown in Table 3, there are six essential parameters and
properties needed to predict the EC. In the original derivation of
all models, the solvent (or solution) thermodynamic properties
have been assumed to be only temperature-dependent and
independent of salt (or ion) concentration. Although it has been
shown that a concentration-dependent static permittivity can
improve the predictions of activity coefficient models,43−46 in
this study, pure solvent properties are used in all predictions.
The investigation of the effect of using concentration-
dependent static permittivity and viscosity will be part of the
subsequent study. In addition, for the temperature dependency,
we have used three correlations for viscosity, 47 static
permittivity,48 and density,48 as shown in eqs 20−22 (the
correlation parameters and range of applicability are shown in
Tables 4 and 5).
ji η zy
lnjjjj zzzz = a1(T − T0) + a 2(T − T0)2 + a3(T − T0)3
k η0 {
+ a4(T − T0)4 + a5(T − T0)5
β1 NAδ 2 ij ρ(T ) ρ(T0) yzz
jj z × 103
j
2 ε0kBMW jk T T0 zz{
εr(T ) = εr(T0) + − fit on experimental data using adjustable parameters, we have
pubs.acs.org/IECR Article
η0 = 1.002 × 10−3 Pa s
a3 a4 a5
−1.7056449 × 10−6 1.41668775 × 10−8 −5.97695538 × 10−11
ρ(T ) = (0.99984 + 1.51782 × 10−4ΔT
− 4.50573 × 10−5ΔT1.55) × 1000 (22)
Table 5. Parameters and Range of Applicability of the Static
Permittivity of Water Correlation48
εr(T0) = 87.82 β1 = 3.1306 δ = 8.33 × 10−30 C m
T0: 273.15 K T: 273.15−373.15 K ρ(T0) = 999.84 kg/m3
One of the essential properties in the context of equivalent
conductivity is the equivalent conductivity at infinite dilution
(ECID) (Λ0(T) or λi0(T)). Since the reduction of the EC with
increasing concentration is a key factor, a reference point is
needed to predict the exact value of the EC. Hence, following the
Debye and Hückel methodology, other authors utilized the
mobility of ions at infinite dilution as the reference of their EC
model. From the theoretical point of view, the salt (or ion)
ECID means that the movement of a single ion under the
(19) influence of an external electric field does not include the effect
of other ions. From the experimental point of view, it means that
we need the extrapolated value of the EC versus the square root
of concentration at zero concentration.
Despite its importance, there are very few models that can
predict ECID. These models are primarily correlations or
semiphenomenological and more or less require experimental
data. In this manuscript, as proposed by Fraenkel,49,50 we have
fitted the experimental data of ionic conductivity at infinite
(εrT )2
dilution (ICID) versus a lumped expression ( ). Moreover,
η
we have used the experimental data directly at temperatures that
ICID experimental data are available (representative curves are
illustrated in Figure S1).
All models except for the DHOLL have a salt-specific or ion-
specific size parameter (R/a/di). For DHOEE and QV, or other
RPMs, this parameter is salt-specific and named the distance of
closest approach (a). For MSA (full or the simple version) and
for DHOSiS, this parameter is ion-specific (di).
Although the physical essence of this parameter is clear, there
are some controversies regarding the exact value to be used in
the EC models. Fraenkel49,50 proposed an electric scale for the
ionic radii calculated based on EC data. Still, in the DHOSiS
model,34 he employed the ionic radii calculated as a fitting
parameter based on activity coefficient data (activity scale)
rather than the electric scale. Onsager and Fuoss8,11−18,51
proposed that the distance of closest approach should be used as
an adjustable parameter. Bernard et al.31 have suggested
crystallographic ionic radii in their MSA-based model. Other
researchers have recommended an effective ionic radius, which
is concentration-dependent and should be estimated based on
correlations.32,52
(20) Using the size parameter (R/a/di) as an adjustable parameter
probably improves the results of EC models. Nevertheless, since
the aim of our study is not to analyze the ability of EC models to
used with all models the crystallographic ionic radii (for the
(21) distance of closest approach (a = r+ + r−)) in the aqueous
3172 https://doi.org/10.1021/acs.iecr.1c04365
Ind. Eng. Chem. Res. 2022, 61, 3168−3185
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Figure 1. Summary of the number of data points and concentration range in the created database for 126 different electrolytes (numbers show the
number of data points, and the color map shows the maximum concentration at 25 °C in mol/L).55−77

Figure 2. Molar conductivity of (a) KCl (1:1), (b) Li2SO4 (1:2), (c) Cu(NO3)2 (2:1), (d) ZnSO4 (2:2), (e) LaCl3 (3:1), and (f) K3Fe(CN)6 (1:3)
predicted by DHOLL, DHOEE, DHOSiS, MSA, MSA-Simple, and QV models versus square root of ionic strength at 25 °C (acronyms 2016-HR-
SBH,55 1970-PM-CCCC-b,58 1984-TI-JCED,66 and 2008-BMR-JCED76 show the references for the collected data points).

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solutions that have been reported by Marcus.53 (The ionic
radius of the salts studied in this work are tabulated in the Table
S1.)
The last model parameter that has been used in the MSA-
based models is the diffusion coefficient at infinite dilution
(D0(T)). Although it has been mentioned that this is a
disadvantage for these models,34 it should be stated that this
parameter can be calculated from ICID (eq 23). Thus, it is not
an extra parameter in the MSA-based EC models.
Di0(T ) RT
0
=
λ i (T ) ZiF 2 (23)
Finally, it should be noted that this study aims to assess the
predictive abilities of the EC models. Thus, besides the ICID, no
fitting parameters are used in this study. The ICID is also
obtained from experimental data reported in the literature.54,55
At temperatures where the experimental data are not available, a
2
linear interpolation method for λ0i versus (εrT ) is used (for more
η behavior at medium to high concentrations is unphysical or at
information, see Table S1 and Figure S1). At temperatures that
ICID data are available, the experimental data are used.
Furthermore, in this study, we treat the ICID as an ion-specific
parameter. Thus, the same value of ICID is used for ion Mν+ or
ion Aν− in different salts contain it.
3. RESULTS AND DISCUSSION
A comprehensive database containing the molar conductivity of
126 electrolytes up to high concentrations and high temper-
atures has been compiled and used in the validation of the EC
models. To this aim, we have created a database of 126 different
electrolytes. This database includes the experimental data from
23 references (as mentioned in Figure 1). Furthermore, ref 55 is
a collection of experimental data for EC of electrolyte solutions
collected from 145 resources. A summary of the database is
depicted in Figures 1 and S7. We have employed this database
for our subsequent investigation of graphical insight and error
analysis.a
3.1. Graphical Comparison of the Predictive Results of
EC Models. All models strongly depend on the system’s
temperature and salt concentration introduced in them
explicitly. Additionally, temperature affects the conductivity
through static permittivity, viscosity, and ECID. This section
analyzes the influence of the system’s temperature and salt
concentration by illustrating the molar conductivity of different
electrolytes versus the square root of ionic strength (SRIS) and
temperatures. We have performed this comparison with the
parameters tabulated in Table S1.
3.1.1. Concentration Dependency. In this section, the molar
conductivityb of 10 different electrolytes (1:1, 1:2, 1:3, 1:4, 2:1,
2:2, 2:3, 2:4, 3:1, 3:2) at 25 °C in water has been investigated,
and the results are plotted against the SRIS. Since the
experimental data are abundant, we have chosen this temper-
ature. Therefore, we can assess EC models for more salts and
over a broader concentration range. The experimental data used
in this section have been taken from the compiled database and
have been treated equally, despite coming from different sources
(for more information on the original papers, see ref 55).
The core purpose of this section is to evaluate the accuracy
and reliability of EC models at a wide range of concentrations
from a graphical point of view. Moreover, we have selected 10
electrolytes to indicate the ability of EC models for different
electrolyte types.
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Figures 2 and S2 present the molar conductivity of these 10
electrolytes versus SRIS. For most 1:1 electrolytes such as KCl
(Figure 2a), the models’ predictions are more satisfactory than
other electrolytes. The MSA and MSA-Simple models provide
very good predictions up to 1.5 M, which is in accordance with
the original papers.31,33 Similarly, QV and DHOEE are close to
the experimental data. Moreover, DHOSiS has been shown to
have a minimum value at low to medium concentrations. After
that, the molar conductivity increases with the SRIS. Although
the intensity of this behavior differs significantly in the various
electrolytes, it can be seen in all of them. It should also be
remarked that Fraenkel discussed about the maximum
concentration that this model is valid, and this behavior is
beyond that concentration limit.34
In addition, we have analyzed the experimental data of more
than 126 electrolytes at different temperatures. However, we
have not seen such behavior in the experimental data of any of
these electrolytes with increasing molar conductivity at higher
concentrations. Therefore, it can be stated that the DHOSiS
least unexpected. Aside from that, in most cases, DHOSiS shows
relatively satisfactory results at low concentrations (LC: c = [0,
0.3] mol/L).
For 1:2 electrolytes (Figure 2b), the models’ predictions are
quite unsatisfactory, but it can be observed that DHOEE, MSA,
and MSA-Simple models are more suitable than the other
models. However, experimental data are only available up to
0.65 mol/L (see Figure 1 or Table S6). For 1:3 electrolytes, the
predictions of DHOSiS at LC are more satisfactory than others.
At LC and medium concentrations (MC: c = [0.3, 1] mol/L),
DHOEE results are acceptable.
Furthermore, for the 2:2 sulfates (Figure 2d), MSA and MSA-
Simple results are not satisfactory even at LC. For these
electrolytes, we have realized from experimental data that the
molar conductivity decreases very fast with √I at LC, but the
reduction slows down at MC and high concentrations (HC: c >
1 mol/L). None of the models could predict this trend, but at
low concentrations, QV and DHOSiS could predict the slope of
data better than others.
In addition, 2:2 sulfates are considered in the literature as
associated electrolytes.3,4,33 For these electrolytes, Apelblat4
could predict the conductivity in dilute solutions (up to 0.05
mol/L) using the QV model and Λ0, KA, and a as fitting
parameters. Chhih et al.33 also could estimate the EC of ZnSO4
up to 1 mol/L using the MSA-Simple model and KA and di as
fitting parameters. Additionally, Turq et al.5 could predict the
equivalent conductivity of MgSO4 up to 1 mol/L using the MSA
model and the KA and average distance parameter as fitting
parameters.
On the other hand, Anderko et al.32 stated that using a
concentration-dependent effective ionic radius, the predictions
of the MSA model can be improved even up to 30 mol/kg for
NaCl, KCl, NaBr, KBr, NaI, KI, MgCl2, AgNO3, NH4NO3,
HNO3, and HCl in water without ion pairing. However, in their
methodology, a six-parameter equation has been proposed for
the concentration-dependent ionic radius, which should be
fitted to the experimental EC data.
Unlike the electrolytes shown in Figure 2, the salts of Figure
S2 have been less frequently analyzed in the context of EC.
Nevertheless, based on the data from our comprehensive
database, we can investigate the performance of the EC models
in these less ordinary electrolytes (2:3, 3:2, 2:4, and 1:4). As can
be seen from Figure S2a, the QV model could predict the
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Figure 3. Molar conductivity of KNO3 at (a) low concentration, (b) medium concentration, and (c) high concentration predicted by DHOLL,
DHOEE, DHOSiS, MSA, MSA-Simple, and QV models versus temperature up to 100 °C (data points are from ref 55).

conductivity at LC. However, at MC that data were available, the
predictions of all models are not satisfactory. For 1:4
electrolytes, the results of DHOEE and DHOSiS at LC are
more acceptable compared to the other models.
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On the other hand, the predictive trends of MSA-Simple are
better than other models. For 3:2 and 2:4 electrolytes (Figure
S2b,c), none of the models’ predictions are close to the
experimental data, even at LC. Another important note is that
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Figure 4. Molar conductivity of BaCl2 at (a) low concentration, (b) medium concentration, and (c) high concentration predicted by DHOLL,
DHOEE, DHOSiS, MSA, MSA-Simple, and QV models versus temperature up to 100 °C (data points are from ref 55).

for all salts in this figure, experimental data decrease fast with √I
at LC, while the reduction slows down at MC.
Finally, for 2:4 and 1:4 electrolytes, the MSA curve like
DHOSiS indicates an unphysical behavior that the molar
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conductivity increases with √I. For some electrolytes such as
LaCl3, the MSA model prediction is not a number at HC. We
have inspected the reason for this behavior in the MSA
formulation. Based on our investigation, omitting the expression
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Figure 5. Molar conductivity of K4Fe(CN)6 predicted by (a) MSA-Simple and (b) DHOEE at different concentrations versus temperatures up to 100
°C (data points are from ref 55).
Figure 6. Molar conductivity of NaNO3 predicted by (a) MSA-Simple and (b) DHOEE at different concentrations versus temperatures up to 100 °C
(data points are from ref 55).
Γ 2d 2 in eqs S12 and S15 solves this problem. Figure S6
compares the result of three versions of the MSA model, full
MSA,31 modified MSA,32 and simple MSA.33 The only
difference between the full MSA and modified MSA is that in
the modified MSA, the expression Γ 2d 2 is ignored.
As shown in Figure S6, using the modified MSA model
completely solves the problem of full MSA model at HC. In
contrast, at LC, the results of modified and full MSA are quite
close together. Thus, ignoring this expression at LC can be
justified due to a lack of numerical importance. However, at MC
or HC, this justification is no longer valid.
3.1.2. Temperature Dependency. In this section, we study
the effect of temperature in three different ways. First, we plot Λ
versus T for six models and experimental data at one specific
concentration including concentration at LC, MC, and HC
(Figures 3 and 4). Next, we present graphically Λ versus T at
different concentrations, and their corresponding experimental
data for DHOEE and MSA-Simple (Figures 5 and 6). Finally, we
show the Λ versus √I semilog plots at different temperatures for
DHOEE and MSA-Simple (Figure 7).
Figures 3 and 4 show the molar conductivity of KNO3 and
BaCl2 predicted by DHOEE, DHOLL, QV, MSA-Simple, and
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DHOSiS. As can be seen from Figures 3a and 4a, at LC, all
models perform, as might have been expected, similarly and in
agreement with the experimental data. It may not raise that
much surprise because deviation from the molar conductivity at
infinite dilution is insignificant at low concentrations. Thus,
Figures 3a and 4a confirm that an accurate value of the molar
conductivity at infinite dilution has been used.
On the other hand, the predictions deviate from experimental
data at higher concentrations (Figures 3b,c and 4b,c). For
KNO3, as shown in Figure 3c, DHOEE, DHOSiS, QV, and
MSA-Simple could predict the molar conductivity at 0 °C.
However, with increasing temperature, the deviation from
experimental data for these models increases. It is also observed
that the results of MSA-Simple and QV models are closer to the
experimental data.
Furthermore, in this analysis, BaCl2 has been chosen to
illustrate how temperature and concentration can affect the EC.
For this system, MSA-Simple can accurately predict its molar
conductivity up to 1 mol/L31,33 (Figure S5). Thus, analyzing the
temperature dependency of this electrolyte can be relevant for
studying both effects. As can be seen from Figure 4b,c, even
though all models except MSA-Simple start to deviate from
experimental data at higher temperatures in 0.25 and 1 mol/L,
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Figure 7. Molar conductivity of (a) KCl, (b) Na2SO4, (c) Ca(NO3)2, and (d) ZnSO4 predicted by MSA-Simple at different temperatures versus square
root of ionic strength (data points are from refs 55, 57, 59, 60, 66, 76, and 78).
the predictions of MSA-Simple are rather accurate. Con-
sequently, it can be implied that the role of concentration
dependency in the prediction of EC models may be more
important than temperature.
By comparing Figures 5a,b and 6a,b, it can be concluded that
the predictions of MSA-Simple at low temperatures are more
precise than DHOEE (same as the previous analysis). Still, at
higher temperatures, none of the models are in good agreement
with the experimental data.
Finally, by looking at Figure 7, the same conclusion can be
drawn about the MSA-Simple. If the predictions of the MSA-
Simple are accurate at one temperature (for example, EC of
Ca(NO3)2−water system at 298.15 K (Figure 7c)), it is also
accurate at other temperatures. Additionally, the MSA-Simple is
generally more accurate at lower temperatures (Figure 7d).
3.2. Quantitative Assessment of the Accuracy of the
Models. In this section, we have used the absolute average
deviation in percent (AAD %) as an error function to quantify
the accuracy of the models (eq 24). Since the EC models predict
the reduction of equivalent conductivity from its value at infinite
Λ electrolytes (Figure S7a,b,f), the DHOEE, QV, MSA, and
dilution, we have chosen ( ) as the main expression in this
Λ0
analysis.
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ÅÄÅ É
ÅÅ 1 Λ pre ÑÑÑÑ
AAD % = ÅÅÅ − 0 ÑÑÑ × 100
ÅÅ N Λ ÑÑÑÖ
N Λexp
ÅÇ
∑
1
Λ0 (24)
We have structured this analysis into two parts. In part one, we
present the AAD% (or error) with the concentration in figures of
AAD% versus √I (Figure S7). In the second part, we categorize
electrolytes based on their anions and the valence type of their
cations. Then, we present the AAD% of the EC models in three
concentration ranges, namely, LC, MC, and HC (Figure 8).
3.2.1. Error Evolution with Concentration. Figure S7
presents the AAD% of six electrolytes for six EC models versus
√I. These graphs can be used to analyze the accuracy and
reliability of models over a wide range of concentrations. The
experimental errors also should be considered.
In terms of accuracy, as shown in Figure S7, it is impossible to
make a general comment for all electrolytes over the whole
concentration range. However, it can be seen that the error of
models up to HC is lower for 1:1 electrolytes.
As can be observed, AAD% increases with the concentration
for all electrolytes and all models. Additionally, for 1:1
MSA-Simple can be said to be moderately accurate with the
AAD% of less than 10% at all concentrations.
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Figure 8. AAD% of DHOLL, DHOEE, DHOSiS, MSA, MSA-Simple, and QV models in low concentration, medium concertation, and high
concentration for (a) MCl, (b) MCl2, (c) MCl3, (d) MSO4, (e) M(ClO4)2, and (f) MNO3 aqueous solutions at 25 °C (M shows the corresponding
cation with different valence type).55−77

Moreover, for 2:1, 2:2, and 3:1 electrolytes, the models,
especially DHOSiS, behave differently at LC from MC/HC. For
3:1 and 2:1 electrolytes (Figure S7c,e), the DHOSiS error at LC
is slightly less than MSA and MSA-Simple. However, at MC and
HC, MSA and MSA-Simple perform better and rather
accurately. Finally, for 2:2 sulfates, DHOSiS is the most accurate
model up to LC (in agreement with the original paper34).
However, the error escalates very rapidly to more than 100% at
higher concentrations.
Another characteristic that can be deduced from these graphs
is reliability, i.e., general performance of the models over a wide
range of concentrations. The errors of DHOSiS and DHOLL
increase rapidly with increasing concentration. On the other
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hand, MSA-Simple and DHOEE are two models whose errors
up to high concentrations are approximately constant or
increase only moderately (Figure S7).
3.2.2. Error Analysis of Electrolyte Families. We have
categorized electrolytes based on their anion and ZCation because
the behavior of the experimental data is quite similar when
electrolytes are grouped in this way. Then, we have calculated
the error of EC models at LC, MC, and HC. The results for six
categories, including salts of type, MCl, MCl2, MCl3, MSO4,
M(ClO4)2, and MNO3, are shown graphically in Figure 8.
For MCl, MCl2, and MNO3, as shown in Figure 8a,b,f, the
models’ predictions except for DHOLL are satisfactory at LC
and MC. In contrast, the errors of MCl2 and MNO3 are generally
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Figure 9. Relaxation term and electrophoretic term of six models for KCl predicted by DHOLL, DHOEE, DHOSiS, MSA, MSA-Simple, and QV
models versus square root of ionic strength at 25 °C.
higher than that of MCl. Moreover, the deviations of DHOSiS at
HC are increased considerably compared to LC and MC.
Unlike MCl and MCl2, that up to MC, acceptable results can
be achieved by DHOEE, MSA, MSA-Simple, DHOSiS, and QV
models, for MCl3 (Figure 8c), only MSA and MSA-Simple yield
rather accurate results. For 2:2 sulfates and 2:1 perchlorates
(Figure 8d,e), the DHOSiS model performs very well at LC, but
again the deviations increase significantly, while DHOEE, MSA,
and MSA-Simple perform better than the other models even at
HC.
Due to experimental errors, the slight differences between
many EC models cannot help provide definite conclusions on
which model is superior. For instance, the difference between
DHOEE, MSA, MSA-Simple, and DHOSiS at LC should be
ignored for 1:1 electrolytes.
In conclusion, it can be stated that DHOSiS predictions are
accurate at LC, but the errors start to grow rapidly with the
concentration, both at MC and HC. Despite their simple
formulation, predictions of DHOEE and MSA-Simple are
acceptable in all cases except for 2:2 sulfates, where the errors
of other models are also high. Furthermore, the error results of
MSA compared to MSA-Simple indicated that from the practical
point of view, there are no advantages for MSA over MSA-
Simple, and the simpler version of MSA could be used without
any loss of accuracy. Moreover, although the QV model has
considered the higher terms of Onsager’s continuity equation, as
Figure 8 indicates, QV does not provide improved results
compared to DHOEE.
We have also presented the arithmetic average of AAD% for
EC models (Table S2). To avoid introducing bias from
electrolytes with more experimental data points, the arithmetic
average is calculated. Thus, the contribution of all electrolytes
with the same valence types to the reported values in Table S2 is
the same.
It can be concluded from Table S2 that for 1:1 electrolytes,
almost all models’ performances are acceptable. For 2:1
electrolytes, DHOEE, MSA, and MSA-Simple, and for 3:1
electrolytes, MSA and MSA-Simple are the best models. Even at
LC, the predictions of all models for 1:4, 2:3, 2:4, and 3:2
electrolytes are not satisfactory. The predictions at MC and HC
also are not in good agreement with experimental data for 2:2
electrolytes.
Finally, it should be noted that the EC models are derived by
some simplifying assumptions. These assumptions result in a
limit to the concentration range that they can be used reliably.
The concentration limits of DHOLL, DHOEE, DHOSiS, MSA,
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MSA-Simple, and QV for 1:1 electrolytes are 10−2, 10−1, 10−1, 1,
1, and 10−1 mol/L, respectively. In addition, the concentration
limit of the EC models might be increased by adjusting the ion
size parameter with the EC experimental data and considering
the ion−ion association using the mass action law (see refs 5, 32,
33, 56, and 74−77). However, there is a possibility for overfitting
to experimental data with an unphysical value for ionic radii
(negative ionic radii as mentioned the Table 3.10 in ref 79) or
the association constant. Hence, in the judgment of the EC
models, their concentration limit should be considered.
3.3. Evaluation of the Relaxation and Electrophoretic
Terms. As mentioned before, two terms contribute to the EC of
electrolytes, the relaxation term and the electrophoretic term. In
this section, we analyze EC models individually by considering
the behavior of their relaxation and electrophoretic terms. Some
results are shown in Figure 9.
From the formulation of DHOLL, it can be easily understood
that the relaxation term and electrophoretic terms are linearly
dependent on √I through the κ (Figure 9). Additionally, for all
electrolytes, the electrophoretic term, and for most of the
electrolytes, the relaxation term of DHOLL have values lower
than for the other models. Contrary to DHOLL, the relaxation
and electrophoretic terms of DHOEE are not linear versus √I,
and for most of the salts, an upward curvature can be seen.
The relaxation term of the QV model has the shape of a
rotated S. At LC, it is very close to the DHOLL, then at MC, the
reduction of ΔX slows down and then sharply increases. The
X
behavior of the electrophoretic term of QV for both cations and
anions is quite similar. There is a minimum in the electro-
phoretic term for almost all electrolytes, but the minimum
position is different. Physically, it means that the movement of
ions under the external electric force first accelerates and then
slows down when the concentration increases (without
considering the relaxation pulling effect in the opposite
direction). This behavior of the QV model cannot be seen
from Λ versus √I because it compensates with the relaxation
term.
The trends of MSA and MSA-Simple are rather similar, and in
most cases, their relaxation and electrophoretic terms are close
to each other. Furthermore, the contribution of the relaxation
term compared to the electrophoretic term is smaller in terms of
the reduction of EC. For all electrolytes, the relaxation term is
higher than at least −0.4, even though there are some cases that
the electrophoretic term is lower than −1. The relaxation term of
MSA-Simple shows a minimum in some cases, but it becomes
almost constant after the minimum. In addition, the relaxation
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term of MSA in some cases and at higher concentrations starts to
increase very fast to reach a positive value (as shown in Figure
S4). It should be mentioned that the positive value for relaxation
term means that the asymmetry of ionic cloud pushes the central
ion parallel to the external electric field, which is not physically
correct.
In Section 3.1, we concluded that the predictions of the
DHOSiS model at medium to high concentration are not
satisfactory, and the trend of the model appears to be
nonphysical at such concentrations. Here, by analyzing the
relaxation and electrophoretic terms, we can explain this
behavior of the model. The cation’s relaxation and electro-
phoretic terms demonstrate a minimum, becoming positive at
MC and HC. It can be attributed to a possibly unphysical
estimation of the ionic cloud size for cations (the smaller ion),
which start to increase with the concentration at a specific point
depending on the electrolyte.
Furthermore, the relaxation term of the DHOSiS model,
unlike other models (even MSA, which is a UPM), is ion-
specific. Following the mathematical procedure used for MSA
proves that even assuming different sizes for anions and cations
leads to a salt-specific relaxation term. However, replacing the
ionic cloud size (κ−1) with an effective size (Ψi*) causes an ion-
specific relaxation term that should be justified. Consequently, it
can be implied that the ion-specific relaxation term is
scientifically inconsistent, or at least for the positive ion, it
needs significant improvements.
Another comment that can be made about the DHOSiS
model is the derivation procedure of the mathematical
formulations for the EC. How the model is derived is not
entirely clear in the original paper.34 Moreover, all other models
(except DHOSiS) have used the same procedure to derive the
formulation for the EC.
Nevertheless, for DHOSiS, it has been explained that three
changes have been made to improve the DHOLL based on “the
smaller ion shell” theory. Thus, unlike the other models, it can be
inferred that Fraenkel has not actually derived the formulation
based on a solution of Onsager’s continuity equation or by
considering the movement of ions and ionic cloud in a viscous
medium.
It appears that DHOSiS has been derived based on the
formulation of DHOEE, which is indeed an improvement
compared to DHOLL, simply by dividing the formulation for
equivalent conductivity by 1 + κa. However, the derivation
procedure of DHOEE includes considering the movement of
ions under the external electric field in a viscous medium and
considering the hindering effect of relaxation term by solving the
Onsager’s continuity equation (see refs 37 and 41 as well as the
Supporting Information). After eliminating the higher-order
terms of κ in the relaxation and electrophoretic terms, DHOEE
can be derived. As a result, if the same procedure is used without
assuming the same ion size, a new formulation could be derived
that improves DHOEE from RPM to UPM. However, it is
unclear that DHOSiS, which explicitly has the ion-specific size
parameter, is derived in this way.
Besides the derivation procedure, the following remarks can
be said about the DHOSiS model. First, the results show that the
DHOSiS model is unreliable at MC and HC because of a
nonphysical behavior. Second, this behavior results from a
nonphysical prediction of the radius of the ionic atmosphere
around the s-ion (Figure 3 in ref 34). Fraenkel mentioned that
“the minimum in the “DH-SiS, s-ion” curve is unphysical, but it
is beyond the c limit of the DHO (and DHOSiS) model.” The
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theory also imposes a concentration limit for the DHOEE and
MSA-Simple models. However, none of them show a non-
physical behavior beyond their concentration limit. On the other
hand, Figures S7 and 8 and Table S2 show that their predictions
are pretty acceptable for some electrolytes beyond their
concentration limits.
Thirdly, the original paper uses the ionic radii from the fitted
value to the activity coefficient data using the DHSiS model
(activity scale).34 In this paper, we have not used the ionic radii
proposed by the author for two reasons. First, these ionic radii
are not reported for all of the cations and anions (only reported
for 11 cations and 7 anions34). As a result, if we used the activity
scale, the EC could not be predicted for many electrolytes.
Second, a fair analysis could not be performed due to the
employment of activity coefficient experimental data in one
model.
4. SEMIPHENOMENOLOGICAL APPROACHES
In this study, we have employed a predictive approach by
minimizing the number of fitting parameters of EC models to
one parameter, which is the ECID. However, in the literature, a
semiphenomenological method is suggested. Fuoss51 suggested
that the EC models of form eq 1 are three-parameter models as
Λ = Λ(a, KA, Λ0). He and colleagues tried to fit their EC models
for symmetrical electrolytes to experimental
data.8,10−18,21,30,80,81 But they barely went beyond the medium
to high concentrations. On the other hand, some of the authors
have utilized Λ0, J1, and J2 as fitting parameters for aqueous and
nonaqueous solutions.3,21,82,83
Furthermore, Apelblat has used the QV as a three-parameter
model and analyzed it for a broad range of aqueous and
nonaqueous electrolyte solutions.4,84−90 Despite the assessment
of many electrolyte solutions, he focused on dilute or even very
dilute solutions. MSA and MSA-Simple models also have been
used to fit the experimental data with the help of an association
model or a concentration-dependent ionic radius.5,20,32,33,52,91
In conclusion, it can be expressed that the EC models can be
treated so that their ability to represent experimental data is
enhanced up to very high concentrations at the expense of fitting
parameters. The literature has primarily used three fitting
parameters, even for nonprimitive models,92 including ECID,
association constant, and a size parameter. However, the
employment of fitting parameters should be theoretically
justified. Therefore, a physically sound methodology is required
that considers not only the accuracy of the predictions but the
acceptable range of the fitted parameters. This methodology
should consider a concentration-dependent static permittivity,
viscosity, and ionic radius as well as ion−ion association with the
help of a reliable EC model, which is the objective of our
subsequent study.
5. CONCLUSIONS
In this paper, six conductivity models have been analyzed with
the help of an extensive experimental database. The predictive
ability of these models is examined for different types of
electrolytes over a wide range of concentrations and temper-
atures. Graphical insight, error analysis, and term-by-term
examination have been utilized to evaluate them in terms of
accuracy, reliability, model dependency, and model implemen-
tation.
From the accuracy point of view, it can be concluded that the
predictions of MSA-Simple, MSA, and DHOEE are more
https://doi.org/10.1021/acs.iecr.1c04365
Ind. Eng. Chem. Res. 2022, 61, 3168−3185
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Table A1. Nomenclaturea

dim(Q) = LaMbTcIdθeNfJg
quantity name a b c d e f g SI
a distance of closest approach 1 0 0 0 0 0 0 m
A surface area 2 0 0 0 0 0 0 m3
b+, b co-ion distances of closest approach 1 0 0 0 0 0 0 m
ci concentration −3 0 0 0 0 1 0 mol/m3
d, di ionic diameter 1 0 0 0 0 0 0 m
Di, D0i diffusion coefficient 2 0 −1 0 0 0 0 m2/s
e elementary charge 0 0 1 1 0 0 0 sA
F Faraday constant 0 0 1 1 0 0 0 sA
G electrical conductance −2 −1 3 2 0 0 0 s3 A2/(m2 kg)
I ionic strength, I = 1/2∑Ni ciZ2i −3 0 0 0 0 1 0 mol/m3
kB Boltzmann constant 2 1 −2 0 −1 0 0 m2 kg/(s2 K)
KA association constant 3 0 0 0 0 −1 0 m3/mol
l length 1 0 0 0 0 0 0 m
NA Avogadro number 0 0 0 0 0 −1 0 mol−1
ri ionic radius 1 0 0 0 0 0 0 m
T temperature 0 0 0 0 1 0 0 K
λi0
t0+, t0− transference number, ti0 = 0 0 0 0 0 0 0
λ−0 + λ+0

Zi ionic valence 0 0 0 0 0 0 0
Γ MSA screening parameter −1 0 0 0 0 0 0 m−1
ε0 vacuum permittivity −3 −1 4 2 0 0 0 s4 A2/(m3 kg)
εr relative permittivity 0 0 0 0 0 0 0
η viscosity −1 1 −1 0 0 0 0 kg/(m s)
e2
κ 2
Debye length, κ = ε0εrkBT
∑k ρk Zk2 −1 0 0 0 0 0 0 m−1
κq −1 0 0 0 0 0 0 m−1
λi, λ0i ionic molar conductivity 0 −1 3 2 0 -1 0 s3 A2/(kg·mol)
Λ, Λ0 molar conductivity 0 −1 3 2 0 -1 0 s3 A2/(kg.mol)
ρi number density of ions −3 0 0 0 0 0 0 m−3
σ specific conductivity −3 −1 3 2 0 0 0 s3 A2/(m3 kg)
υi stoichiometric coefficient 0 0 0 0 0 0 0
a
L, length; M, mass; T, time; I, electric current; θ, absolute temperature; N, amount of substance; J, luminous intensity.

accurate than those of the other models. However, at lower

concentrations, the DHOSiS model reveals more precise
■ APPENDIX
For definitions of quantity terms, see Table A1.

■
predictions compared to the experimental data. Likewise,
MSA-Simple and DHOEE are more reliable than other models.
ASSOCIATED CONTENT
There are two reasons for this. First, their error increases less
rapidly than for other models with the concentration. Second, *
sı Supporting Information

we have never observed any nonphysical behavior in their
predictions. In addition, MSA-Simple provides more acceptable
predictions of the equivalent conductivity at lower temperatures
compared to the other models.
The predictions of the DHOSiS in medium to high
concentrations display a minimum that cannot be physically
or theoretically justified. Moreover, term-by-term analysis
indicates that the minimum stems from a specific behavior of
the size of ionic cloud around the cation (the smaller ion), which
leads to an unphysical estimation of the relaxation and
electrophoretic terms. In addition, the property or parameter
dependency of almost all EC models is the same. They all require
molar conductivity at infinite dilution, solvent viscosity, solvent
relative permittivity, and ionic radius.
Finally, the possible improvement for the EC models may be
adopting a semitheoretical approach. It includes but is not
limited to using the ionic radius as an adjustable parameter,
considering ion−ion association, and employing a concen-
tration-dependent static permittivity.
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.1c04365.
Parameters needed for the EC models; average error of
equivalent conductivity models, regressed curves of ICID
versus the lumped expression for Cl−, K+, (SO4)2−, La3+,
Z2+, Ba2+, H+, and (NO3)− ions; molar conductivity of
Ca3(Fe(CN)6)2, La2(SO4)3, Ca2Fe(CN)6, and K4Fe-
(CN)6 versus square root of ionic strength predicted by
EC models and compared with experimental data; term-
by-term analysis KCl, Li2SO4, Cu(NO3)2, ZnSO4, and
LaCl3; term-by-term analysis of K3Fe(CN)6, Ca3(Fe-
(CN)6)2, La2(SO4)3, Ca2Fe(CN)6, and K4Fe(CN)6;
comparison of three formulations of MSA models
(simple, full, and modified); AAD% evolution of
DHOLL, DHOEE, DHOSiS, MSA, MSA-Simple, and
QV models versus square root of ionic strength; number
of references for each electrolyte; validation of static
permittivity and viscosity correlations of pure water;
complete mathematical formulation of MSA and QV

3182 https://doi.org/10.1021/acs.iecr.1c04365
Ind. Eng. Chem. Res. 2022, 61, 3168−3185
Industrial & Engineering Chemistry Research
models; AAD% of binary electrolyte solutions in water;
and derivation of DHOEE (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Georgios M. Kontogeorgis − Center for Energy Resources
Engineering, Department of Chemical and Biochemical
Engineering, Technical University of Denmark (DTU), 2800
Kgs. Lyngby, Denmark; orcid.org/0000-0002-7128-1511;
Email: gk@kt.dtu.dk
Authors
Saman Naseri Boroujeni − Center for Energy Resources
Engineering, Department of Chemical and Biochemical
Engineering, Technical University of Denmark (DTU), 2800
Kgs. Lyngby, Denmark; orcid.org/0000-0003-2830-8624
Xiaodong Liang − Center for Energy Resources Engineering,
Department of Chemical and Biochemical Engineering,
Technical University of Denmark (DTU), 2800 Kgs. Lyngby,
Denmark; orcid.org/0000-0002-2007-546X
Bjørn Maribo-Mogensen − Hafnium Labs ApS, 1456
Copenhagen, Denmark; orcid.org/0000-0001-5447-412X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.1c04365
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank the European Research Council (ERC) for
funding this research under the European Union’s Horizon 2020
research and innovation program (grant agreement no.
832460), ERC Advanced Grant project “New Paradigm in
Electrolyte Thermodynamics.” They also thank DTU Chemical
Engineering for partial funding of this work.
■
LIST OF ABBREVIATIONS
AAD% absolute average deviation in percent
DHOLL Debye−Hückel−Onsager limiting law
DHOEE Debye−Hückel−Onsager extended equation
DHOSiS Debye−Hückel−Onsager smaller ion shell
EC equivalent conductivity
ECID equivalent conductivity at infinite dilution
FO Fuoss and Onsgaer
HC high concentrations, c > 1.0
ICID ionic conductivity at infinite dilution
LC low concentrations, c = [0, 0.3]
MC medium concentrations, c = [0.3, 1.0]
MSA mean spherical approximation
QV Quint and Viallard
RPM restricted primitive model
SRIS square root of ionic strength
UPM unrestricted primitive model
■
a
ADDITIONAL NOTES
Our database has the salt concentration as molarity, defined as
the moles of salt per volume of solution. However, the
concentration units found in the literature are quite puzzling
so that there are cases in which the molarity is defined as the
mole per liter of the solvent. We have tried to double-check the
reported experimental data to ensure the consistency of units in
3183
pubs.acs.org/IECR Article
the database. However, some of the data points may suffer from
error due to the ambiguity of the concentration unit.
b
To convert the equivalent conductivity predicted by the
models to the molar conductivity, equations in Table 2 are used.
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