E784 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018)

0013-4651/2018/165(14)/E784/9/$37.00 © The Electrochemical Society

Ion-Pair Conductivity Theory V: Critical Ion Size and Range of

Ion-Pair Existence
Andrei Dukhin,1,z Sean Parlia, 2
and Ponisseril Somasundaran2
1 Dispersion Technology Inc., Bedford Hills, New York 10507, USA
2 Columbia University, New York, New York 10027, USA

There are two mechanisms by which ion size affects conductivity of liquids: hydrodynamic resistance, and electrostatic attraction
between cation and anion that leads to the formation of ion-pairs. Increasing ion size reduces conductivity due to growing hydrody-
namic resistance. On the other hand, increasing ion size reduces the probability of ion-pairs formation, which leads to higher ionic
strength and higher conductivity. The opposing nature of these two mechanisms indicates the existence of a “critical ion size” that
corresponds to the maximum conductivity. We apply a theory that was published recently in this Journal with a wide variety of
supporting experimental data for determining value of this “critical ion size”. This theory predicts a very peculiar phenomenon: ions
with sizes that are narrowly distributed around 1 nm (±0.5 nm) must dominate conductivity. This prediction is valid for solutions
with ion-pairs, which according to the theory could occur when relative permittivity is below 10 if ionic strength of the liquids is low
(<10−6 mol/l). This threshold shifts toward higher relative permittivities with increasing ionic strength.
© 2018 The Electrochemical Society. [DOI: 10.1149/2.0821814jes]

Manuscript submitted September 7, 2018; revised manuscript received October 8, 2018. Published November 1, 2018.

When we consider ionization in non-polar media, there are two
mechanisms by which ion size itself impacts the overall conductivity
of the system:
Firstly, ion size determines the hydrodynamic resistance that an ion
experiences whilst moving relative to the surrounding liquid, when un-
der the influence of an electric field. This hydrodynamic resistance is
a function of the interfacial area between the ion and the surrounding
liquid. Hence, larger ions have more interfacial area and thus larger
amounts of hydrodynamic resistance, which limits ion mobility and
therefore decreases conductivity (as conductivity is a function of the
ion mobility). Accordingly, the smaller the ion, the higher the con-
ductivity because of the hydrodynamic resistance.
Secondly, ion size controls the distance of closest ion approach in
ion-pairs1 and, consequently, the intensity of cation-anion attraction
in a potential ion-pair. Smaller ions can approach each other at closer
distances, and therefore the attractive force between them is stronger
when compared with larger ions, which have distances of closest ion
approach which are farther apart. The stronger the attractive forces
between oppositely charged ions, the more likely they are to combine
and form an ion-pair. Consequently, the balance between ions and
ion-pairs shifts toward ion-pairs as ion size decreases. As a result, the
concentration of free ions decreases. An ion-pair is neutrally charged
entity, and accordingly the ions contained within an ion-pair do not
contribute to the conductivity of a system (i.e. they are not “free ions”).
Therefore, this mechanism leads to a reduction of the conductivity
with decreasing ion size, which is opposite to the first mechanism
pertaining to hydrodynamic resistance.
As a result of these opposing trends, the conductivity of a given
non-polar system should have a maximum that is a function of ion
size. The value of this “critical ion size” (dcr ) which determines the
position (and magnitude) of this conductivity maximum is obviously
very important.
There has been some discussion of the role ion size plays with
regards to non-polar conductivity in the literature, for instance in the
extensive review by Prieve et al.2 However, only a limited amount
of the published data is usually discussed, and the critical ion size
that was mentioned above is ignored or omitted entirely. Accordingly,
this paper is dedicated to the theoretical prediction of the value of
this critical ion size and the range of concentrations (i.e. amphiphile
concentrations in nonpolar media) where it is important.
It should be noted that the notion of critical ion size is relevant only
for those liquids where ion-pairs could potentially exist. This issue
is also omitted from the relevant literature, creating the impression
that ion-pairs can exist in any liquid. However, a detailed theoretical
analysis of this subject (presented in this paper) indicates that this
z
E-mail: adukhin@dispersion.com
is not true. The range of liquids that can support ion-pairs is quite
limited, and will be specified here.
In order to examine both critical ion size and range of ion-pair exis-
tence the conductivity theory presented in the paper3 will be used. This
theory has been well-tested experimentally, and accordingly verified,
for a variety of amphiphilic substances that enhance the conductivity
of non-polar liquids.4–6 These experimental tests confirmed unam-
biguously the validity of this theory across the full composition range
of such liquid mixtures. A short overview of these experiments is
presented below.
Conductivity Theory
As we mentioned above, there is a theory3 that describes conduc-
tivity of binary liquid mixtures within the full composition range, from
pure non-polar liquid to pure amphiphile. Here is the final result of
that theory, with equation for conductivity K in units [S/m]:
e2
K = exp
4π2 η (ϕ)de 3 dh

(−λ/de ) ( 1 + 16/3πN A de 3 ϕC A exp (λ/de ) − 1) [1]
where λ is Bjerrum length which depends on relative permittivity ε,
that in turn depends on the volume fraction of amphiphilic liquid ϕ:
e2
λ= [2]
4πε0 ε (ϕ) kT
Other parameters in these equations are:, e is electron charge, ε0 is
vacuum permittivity, NA is Avogadro’s number, T is absolute tem-
perature, k is Bolztmann’s constant, η is dynamic viscosity (which
is also dependent on the concentration of amphiphilic liquid ϕ), de
is distance of closest ion approach in the ion-pair, dh is the effective
hydrodynamic ion size, and CA is the concentration of ions in the pure
amphiphilic liquid.
There are two parameters that are linked to the geometry of the
ions: hydrodynamic ion size dh and distance of the closest ion ap-
proach in the ion-pair de , which determines intensity of cation-anion
electrostatic interaction in the pair.
Hydrodynamic ion size takes into account potential difference
between cation and anion hydrodynamic ion radiuses a+ and a− ,
respectively, according to the following Equation suggested in the
paper:2
4a + a −
dh = [3]
a+ + a−
The relationship between the “distance of the closest approach in
the ion-pair” to ion size is more complicated, because it is known

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 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018)
(via monography by K. Izutsu7 ) that the solvating layers of a cation
and anion can overlap to certain degree when they build an ion-pair.
We follow here the approach suggested, and successfully employed,
by Onsager and Fuoss,8,9 who assumed that hydrodynamic ion size
equals to the distance of the closest approach:
dh = de = d [4]
This assumption allows us to introduce an effective ion size d as a
single geometric property of the ions.
A detailed derivation of this theory, and its relationship with the
Onsager-Fuoss theory,7,8 can be found in the review.10 Its main dis-
tinction from the Onsager-Fuoss theory is application of the Aurbach
equation for ionic strength J11
√ The conductivity of their mixtures with low viscous non-polar liq-
1 + 4M F Ci − 1
J= [5]
2M F
where MF is the Fuoss constant for equilibrium balance between free
ions and ion-pairs,9 and Ci is total concentration of ions in particular
liquid mixture.
The final relationship between nonpolar conductivity and effective
ion size d is expressed below in the following equation:
 uid. Figure 1 presents the conductivity of methanol-toluene mixtures
e2
K = exp (−λ/d) ( 1+16/3πN A d 3 ϕC A exp (λ/d)−1)
4π2 η (ϕ)d 4
[6]
There are 2 parameters that are unknown and not easily measur-
able: ion size d and concentration of ions -or ionic strength- of the
pure amphiphilic liquid CA . These two parameters serve as adjustable
parameters for fitting the experimental data.
This parameterization differs significantly form the classical elec-
trochemical approach, where an added substance (electrolyte) is char-
acterized via molar concentration, dissociation constant, etc. This
classical parametrization is not applicable to non-aqueous electro-
chemistry for several reasons:
First, there is no consensus on the mechanism by which ions form,
and are maintained, in non-polar liquids. The Appendix presents sev-
eral models that might be applicable, but it is not clear yet which one,
if any, is dominant.
Second, the ionic strength of non-polar liquids is many orders of
magnitude lower than that of aqueous solutions. The contribution of
impurities to the total ion concentration becomes important and cannot
be neglected for liquids with an ionic strength below 10−6 mol/l.
Third, it is inadequate to define amphiphilic substances that cause
ionization in non-polar liquids as simply electrolytes. It is possible that
their molecules breakup gives rise to ions, but impurities mentioned
above complicate the quantitative description of this effect.
However, amphiphiles perform a second important function: they
solvate ions. Amphiphiles by definition have a hydrophilic portion
(typically a polar head group) and a hydrophobic (i.e. nonpolar) por-
tion. The attraction between their polar heads and the core electric
charge of the ion creates a steric stabilization layer around ions. In
other words, the molecules of added amphiphilic substance perform
the same role water molecules do in an aqueous solution: They sol-
vate free ions and allow them to remain in solution. The addition of
amphiphilic substance to non-polar liquid enhances solvation of ions.
The first theoretical description of such a “self-solvating” effect by an
amphiphilic substance was given in the review.10
The theoretical model given in Eq. 6 reflects these differences
between aqueous electrochemistry and the electrochemistry of non-
polar liquids. It has already been proven that this theory is valid for a
wide variety of mixtures. The most convincing of these experimental
verification tests are described in the next section.
Experimental Verification of the Conductivity Theory
Experimental verification was conducted for two-component mix-
tures of non-polar liquid and amphiphile, across the full composition
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E785
range from pure non-polar to pure amphiphile. There have been 3 non-
polar liquids tested: toluene, hexane and heptane. The amphiphilic liq-
uids used in these tests includes 8 different alcohols and 4 non-ionic
surfactants.
This selection of amphiphilic liquids allowed for experimental
testing of the roles that permittivity and viscosity, two important pa-
rameters in nonpolar electrochemistry, have in affecting the conduc-
tivity of a nonpolar liquid mixture. Alcohols have low viscosity very
close to the viscosity of the studied non-polar liquids. That is why
the conductivity of alcohol/non-polar mixtures depends mostly on the
composition and permittivity of the mixture. Changes in viscosity as
a function of mixture composition are practically unimportant.
On the other hand, liquid non-ionic surfactants are very viscous.
uids depends strongly on the variation of viscosity with the mixture
composition.
Detailed descriptions of these experiments have already been pub-
lished in the papers.3–6
The role of permittivity: mixtures of alcohols with non-polar
liquid.—The widest range of conductivity variation that was measured
in these experiments was achieved using methanol as amphiphilic liq-
within the full composition range. It is seen that conductivity varies 7
orders of magnitude.
The solid line in the Figure 1 represents the best theoretical fit to
the experimental data (dots) using the model described by Equation 6.
Two adjustable parameters were used: ion size and ionic strength of
methanol. Ion size was found to be equal to 0.63 nm, and the ionic
strength of the methanol that was used in that experiment was found
to be 0.00029 mol/L.
Figure 1 clearly demonstrates that suggested the theory fits the
experimental accurately across the entire concentration range.
Looking more closely at the graph in Fig. 1, there are 2 distinctively
different ranges within this conductivity curve.
At high concentrations of methanol the conductivity is effectively
a linear function of the methanol content. This is true for methanol
concentrations above approximately 30% (by volume). In this range
the relative permittivity of the mixture is high enough to prevent the
formation of ion-pairs. However, conductivity becomes an exponen-
tial function of methanol content below approximately 30%. This is
the sign that ion-pairs are appearing due to the stronger electrostatic
attraction between cations and anions.
At 30% methanol in a methanol-toluene mixture the relative per-
mittivity is roughly equal to 10, as is shown on Figure 2. We can
assume that a relative permittivity of 10 roughly separates the con-
centration range in which ion-pairs exist (<10) from the range that
is free from ion-pairs (>10). If this is true, then higher molecular
weight alcohols, which typically have lower relative permittivities,
must exhibit the transition from linear to exponential dependence of
conductivity at higher alcohol content.
Subsequent measurements confirmed this prediction. Figure 3
presents conductivity dependence curves for all 8 alcohols. It is seen
that the linear range shrinks with decreasing alcohol relative permit-
tivity. It disappears completely for hexanol, heptanol, and octanol,
which have relative permittivities very close to 10.
Quantitative agreement has been also achieved. Figure 1, as previ-
ously stated, presents the theoretical fit based on Eq. 6 for methanol-
toluene mixtures. Similar theoretical fits were observed for all other
studied alcohols-toluene mixtures, as shown in paper.3
Later, similar agreement between theory and experiment was
demonstrated for mixtures of alcohol with 2 other non-polar liquids
(hexane and heptane).4
The role of viscosity: mixtures of non-ionic surfactant with non-
polar liquid.—In order to test the influence of viscosity on the con-
ductivity of liquid mixtures we needed amphiphilic liquids of high
viscosity. Liquid non-ionic surfactants are good candidates for such
a test. Figure 4 shows the viscosity of toluene mixtures with SPAN
 E786 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018)

3
10

2
10

1
10
Conductivity (10E-06 S/m)

0
10

-1 Figure 1. Measured conductivity of binary methanol-

10 Experimental toluene mixture with different alcohol content and theo-
Theoretical retical fit achieved with Eq. 6. Symbols are experimental
-2 data, lines are theoretical fit. Published in the paper.2
10

-3
10

-4
10

-5
10
0 10 20 30 40 50 60 70 80 90 100
Pure Toluene Pure Methanol
Weight Fraction (%)

20 and SPAN 80, which are typical non-ionic surfactants. Since the
viscosity varies 3 orders of magnitude, the impact is has on the con-
ductivity of those systems is quite substantial.
However, the relative permittivity of these mixtures is below 10 in
both cases because the liquid non-ionic surfactants have low relative
permittivities themselves. Therefore, it is expected that the existence
of ion-pairs in these mixtures, and their dependence on the volume
fraction of surfactant, must exhibit the same exponential relationship
that was seen in the alcohols describe previously.
It appears that the viscosity variation masks this exponential depen-
dence on permittivity. This was confirmed by multiplying conductivity
by viscosity, creating the so called “Walden product12 ”. According to
the Eq. 6, such product (conductivity x viscosity) must be an exponen-
tial function of the relative permittivity and, consequently, surfactant
volume concentration.
Figure 5 combines data for all 4 surfactants that we studied. It
is seen that Walden product is indeed an exponential function of the
surfactant content for all four mixtures on a linear scale (i.e. it is
a linear function when plotted on logarithmic scale). This can be
considered as qualitative confirmation of the theory.
Quantitative confirmation was observed for the solutions of all 4
surfactants as well. Figure 6 demonstrates the best theoretical fit for
the conductivity of the toluene mixtures with SPAN 80. A similar fit
was achieved for all 4 surfactants.
There is one peculiar feature of viscosity for these liquid mix-
tures that has an interesting effect on conductivity dependence. As

40
Methanol
Ethanol
Propanol
Butanol
30 Pentanol
Hexanol
Heptanol
Dielectric Constant

Octanol

Figure 2. Measured relative permittivity of binary

20
alcohol-toluene mixtures with different alcohol con-
tent. Lines illustrate trends, they are not theoretical
fits, paper.2

10

0
0 10 20 30 40 50 60 70 80 90 100
Pure Toluene Pure Alcohol
Weight Fraction of Alcohol (%)

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 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018) E787

-3
10

-4
10

-5
10

-6
Conductivity (S/m)

10

10
-7
Figure 3. Measured conductivity of binary alcohol-
toluene mixtures with different alcohol content.
Methanol Lines illustrate trends, they are not theoretical fit.
10
-8
Ethanol Published in the paper.2
Propanol
-9 Butanol
10
Pentanol
Hexanol
-10
10 Heptanol
Octanol
-11
10
0 10 20 30 40 50 60 70 80 90 100
Pure Toluene Pure Alcohol
Weight Fraction of Alcohol (%)

demonstrated in Fig. 4, viscosity is an exponential function of sur- Discussion and Theoretical Predictions
factant volume concentration. Somehow this exponential function
The extensive experimental verification of this theory described
compensates the exponential dependence of conductivity on relative
above justifies using it for deriving theoretical predictions regarding
permittivity, specifically in the range of low volume fraction of the
ion size and the range in which ion-pairs exist in liquids. According
surfactant (i.e., the range in which ion-pairs are present). The result-
to this theory, there are several parameters that affect the conductivity
ing effect is quite peculiar: these phenomena appear to “cancel each
of non-polar liquids mixed with amphiphilic substances:
other out,” and conductivity becomes a linear function of the surfac-
tant content in this concentration regime. This unexplained linearity
r Viscosity of the mixture
is documented in prior research, and several electrochemical models
have been suggested for explaining it.10 Our tests indicate that this
r Permittivity of the amphiphilic material
r Volume fraction of the amphiphilic material
linearity is simply the result of the added exponential dependence of
r Concentration of ions in the pure amphiphilic liquid
viscosity on the surfactant volume fraction. To date there appears to
be no theory that can explain such a phenomenon.
r Ion size

SPAN 20 & SPAN 80: Viscosity vs Surfactant

Concentraon - Log Scale
10000

1000

Figure 4. Measured viscosity for mixtures of SPAN

100 non-ionic surfactants with toluene, published in the
Viscosity (cP)

paper.5
SPAN 20
SPAN 80
10

1
0 20 40 60 80 100

0.1
Wt Fracon of SPAN (%)

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 E788 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018)

K*η vs Surfactant Concentraon

1.00E+00

1.00E-01

1.00E-02

1.00E-03

1.00E-04
K*η

1.00E-05 SPAN 20

1.00E-06 SPAN 80
OFX-5098
1.00E-07
OFX-0400
1.00E-08

1.00E-09

1.00E-10

1.00E-11
0 20 40 60 80 100
Wt. % of Surfactant

Figure 5. Measured conductivity multiplied with measured viscosity for mixtures of SPAN non-ionic surfactants with toluene and for Xiameter surfactants with
toluene, from the papers.4,5 Logarithmic scale.

In order to graphically demonstrate conductivity trends, it is nec-
essary to specify all of these parameters.
As a first step, theoretical “Walden products” (conductivity mul-
tiplied by viscosity) were presented graphically. These plots follow
theoretical predictions, which was alluded to earlier and states that
conductivity multiplied by viscosity has an exponential dependence
on volume fraction when ion-pairs are present, and a linear depen-
dence when they are not. This is discussed in more detail in a previ-
ously published paper on the role of viscosity on the conductivity of
non-polar liquids.12
Next, conductivity was calculated (using Eq. 6) versus ion size
at two ionic strengths (of the liquid mixture) in order to determine a
value for the “critical ion size”. In these calculations ionic strength of
the liquid mixture is the product φ∗ CA in Eq. 6.
Finally, similar Walden products are graphed versus relative
permittivity, in order to examine the range in which ion-pairs
exist.
Critical ion size value.—Figures 7 and 8 demonstrate the depen-
dences of conductivity multiplied by viscosity (Walden product) on

SPAN 80 - Theory vs Experiment

1

0.1
Conducvity (10-6 S/m)

0.01 Figure 6. Measured data and theoretical models for

conductivity of mixtures of SPAN 80 non-ionic sur-
factant with toluene. Symbols are as follows: ( ) –
Measured Data Measured conductivity; ( ) – Theoretical con-
Theorecal Data
ductivity. Published in the paper.5
0.001

0.0001

0.00001
0 20 40 60 80 100
Wt. % of SPAN 80

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 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018) E789

2E-11

1.5E-11

Es = 5
Es = 10
Figure 7. Conductivity multiplied by viscosity ver-
1E-11 sus ion diameter. Ionic strength of the liquid mixture
is 10−8 mol/l. Non-polar liquid relative permittivity
K*η (C2/m4)

Es = 15
is 2.36. Amphiphilic liquid relative permittivities are
Es = 20
shown in the legend.
Es = 25
Es = 30
5E-12

0
0 1 2 3 4 5
Ion Size d (nm)

the ion size. The ionic strength of the liquid mixture is 10−8 mol/L in
Figure 7, and 10−7 mol/L in Figure 8.
Relative permittivity of the amphiphile is not important at lower
ionic strengths, as all curves overlap. The value of the critical ion di-
ameter that ensures the highest conductivity is approximately 1.5 nm.
This is true for all curves in Figure 7, with only slight variation due to
relative permittivity.
Increasing the ionic strength leads to a spreading of the critical ion
size, making it dependent on the relative permittivity of the additive.
However, the range still remains very narrow, from roughly 0.5 nm
up to 1.5 nm.
This simple analysis predicts that ions with diameters that are
closely clustered around 1 nm (±0.5 nm) contribute most to the con-
ductivity of non-polar liquids. These theoretical predictions can be
compared with values of ion size published in literature.
We found 17 papers3–6,15,21–32 that published data on ion size in
non-polar liquids with the addition of various amphiphilic substances,
both solid and liquid. While no claims are made that these papers

4E-10

3.5E-10

3E-10

2.5E-10

Es = 5
Figure 8. Conductivity multiplied by viscosity
Es = 10
2E-10 versus ion diameter. Ionic strength of the liquid
K*η (C2/m4)

Es = 15 mixture is 10−7 mol/l. Non-polar liquid relative

Es = 20 permittivity is 2.36. Amphiphilic liquid relative
permittivities are shown in the legend.
1.5E-10 Es = 25
Es = 30

1E-10

5E-11

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Ion Size d (nm)

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 E790 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018)

14

12

10
Frequency

Figure 9. Frequency of appearance of certain ion

6
diameters in the published paper.

More
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
2.6
2.8
3
3.2
3.4
3.6
3.8
4
4.2
4.4
4.6
4.8
5
ion diameter [nm]

are all encompassing of such data, it seems reasonable to consider below approximately 10 in order to support ion-pairs. This empirical
them representative of the findings on this subject. Some papers prediction is verified in the next section using the abovementioned
present numbers for ion radii, which was converted into ion diam- theory.
eters. It is worth noting that the methods applied for collecting this
data have not been considered, and that differences between anion Range of ion-pairs existence.—Figures 10 and 11 depict theoret-
and cation size were ignored. The purpose here is simply to see if ical Walden products plotted versus the relative permittivity of the
agreement exists between theory and published data on an elementary liquid mixture. The liquid mixture ionic strength is 10−6 mol/L in Fig.
level. 10, and 10−2 mol/L in Fig. 11.
Figure 9 presents these values for ion diameters (in nanometers) The graphs show that for low ionic strength liquids (Fig. 10),
organized as a histogram. It is seen that the published data for ion the relative permittivity value of 10 is indeed the threshold that
sizes is also, for the most part, clustered around 1 nm, which agrees determines the range in which ion-pairs exist, i.e. they could exist
with theoretical prediction formulated above. only in liquids with relative permittivity below 10 in low conducting
As stated earlier, the existence of a critical ion size is due to liquids.
opposing mechanisms, which both affect conductivity and are ion Increasing ionic strength shifts this ion-pair threshold to the higher
size dependent: hydrodynamic resistance, and electrostatic cation- relative permittivity values. Fig. 11 indicates that it becomes close to
anion attraction that leads to ion-pairs formation. 30 in the liquids with a high ionic strength of 10−2 mol/L, which
Critical ion size phenomenon occurs, consequently, only in liquids could correspond to even aqueous solutions. However, it is still well
with ion-pairs. The experiment presented above in the The role of vis- below relative permittivity of 80 which would typically characterize
cosity: mixtures of non-ionic surfactant with non-polar liquid section the dielectric range of aqueous solutions. This implies that ion-pair
indicates that the relative permittivity of the liquid mixture must be existence in aqueous solutions is unlikely.

Figure 10. Conductivity multiplied by viscosity versus relative permittivity of the liquid. Ionic strength of the liquid mixture is 10−6 mol/l. Non-polar liquid
relative permittivity is 2.36. Ion size values are shown in the legend.

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 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018)
Figure 11. Conductivity multiplied by viscosity versus relative permittivity of the liquid. Ionic strength of the liquid mixture is 10−2 mol/l. Non-polar liquid
relative permittivity is 2.36. Ion size values are shown in the legend.
An additional interesting conclusion can be drawn from these re-
sults. There are two known mechanisms for describing ion interaction:
Bjerrums’ ion-pairs and Debye-Huckels’ ion-clouds.32 Our analysis
here confirms that these two mechanisms do not overlap, which justi-
fies their being studied independently. Bjerrums’ ion-pairs dominate
ion interaction in liquids with low ionic strength and low relative
permittivity, whereas the Debye-Huckel effect is important for high
conducting aqueous solutions.
Conclusions
Ion-pairs conductivity theory created in the paper3 and experimen-
tally verified with a variety of liquid mixtures predicts the existence of
a critical ion diameter at which the conductivity of a non-polar liquid
with amphiphilic additive, such as surfactant, alcohol, etc., reaches a
maximum. The value of this critical ion size is approximately 1 nm
± 0.5 nm. This phenomenon of the “critical ion size” reflects the
balance between hydrodynamic resistance and electrostatic attraction
between cations and anions leading to ion-pair formation. These two
effects contribute to the ionic conductivity of the system with the
opposing trends.
Ions with sizes in said range dominate the conductivity of liquid
mixtures that contain ion-pairs, and notion of “critical ion size” is
valid only for such liquids. There is a threshold value for relative
permittivity of the liquid mixture that marks the range of such liquids
that contain ion-pairs. This threshold value is 10 for the liquids with
low ionic strength below 10−6 mol/L, as only liquids with a relative
permittivity below 10 can support ion-pairs at low ionic strength. This
conclusion is supported by both theory and experiment.
This threshold value increases up to approximately 30 for liquids
with high ionic strength (e.g. 10−2 mol/L), which corresponds to aque-
ous solutions. This means that the existence of ion-pairs in aqueous
solutions is unlikely. On the other hand, it also implies that the two
effects of ion interactions, Bjerrum’s ion-pairs and Debye-Huckels’
ion-clouds, do not overlap.
Appendix: Mechanisms of Ion Formation in Non-Polar Liquids
There are two recently published reviews2,10 on the electrochemistry of non-polar
liquids. Both of them present an analysis of the current understanding of the mechanisms
by which ions form and are maintained in non-polar liquids. Both reviews are in agreement
regarding the importance of ion-pair formation in non-polar liquids. On this subject they
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E791
are in consensus with previous studies of non-aqueous electrochemistry conducted in the
early 20th century by Bjerrum, Onsager, and Fuoss.1,8,9 They conclude that the balance
between free ions and ion-pairs is a controlling factor of ionic strength in non-polar
liquids.
Unfortunately, there is no such concurrence on the mechanism that is responsible for
ion formation in non-polar liquids in the first place. Below we present some comments
regarding the variety of models on this subject.
Early works on non-aqueous electrochemistry stressed the importance of electrostatic
interactions between cations and anions due to the low relative permittivity of the non-
polar liquid. This leads to the understanding that ions should have a sufficiently large size
in order to exist as free entities in such liquids. That is why early pioneering works by
Fuoss, Krauss, and Onsager were conducted with large picrate molecules.8,9,13,14 They
assumed that the dissociation of such molecules would yield large ions that could withstand
electrostatic attraction. Effectively, they applied the classical “dissociation model” for
explaining ion formation in non-polar liquids with one additional requirement: that ions
must be sufficiently large.
However, they neglected to discuss the solvation aspect of ionization. There is practi-
cally no discussion about the state of the small counter-ions that split from the large picrate
molecules. The fact that these ions cannot be solvated by the non-polar liquid molecules
due to the lack of molecular dipole moments (in the non-polar liquid molecules) was
simply ignored.
On the other hand, Fuoss and Krauss realized that ion-pairs carry dipole moments
that could lead to the formation of more complicated structures due to ion-dipole and
dipole-dipole interactions. This approach to non-aqueous electrochemistry, based on the
dissociation model, is still being applied in relevant peer-reviewed literature, as can be
seen in recent (2009) publications.15
However, this model ignores the existence of the other objects with dipole moments
in such non-polar solutions: neutral molecules of the added substances. It turns out that
practically all substances that causes ionization of non-polar liquids are amphiphilic. They
must have a sufficiently long carbon chain (hydrophobic) on one side for solubility in
non-polar liquid, and a polar group that is capable of dissociation (hydrophilic) on the
other side. This polar group has a dipole moment, which may play an important role in
ion formation of various structures.
The earliest paper known to us on the subject of the interactions of dipole moments of
added molecules in non-polar liquids is by Nelson and Pink in 1951.16 In that paper they
wrote that “. . . in a non-polar solvent, aggregation is clearly the result of a balance between
the solubilizing power of the hydrocarbon chains and the attractive forces between polar
parts of the soap [surfactant] molecules. . . ” They also wrote that “. . . Like the coulombic
force between ions, the attractive force due to the dipoles is exerted indiscriminately on
all other polar molecules depending only on the distance of separation. . . ”
This dipole-dipole interaction leads to the formation of “inverse micelles” in non-
polar liquids, which is supported by many detailed experimental studies. These “inverse
micelles” are neutral entities. However, it is possible that could become charged some-
times.
According to Morrison,17 a paper by Mattoon and Mathews from 194918 was the
first to mention “charged inverse micelles”. They discovered that AOT micelles behave as
positively charged particles. The mechanism describing this charging of inverse micelles
E792 Journal of The Electrochemical Society, 165 (14) E784-E792 (2018)
is called the “disproportionation model”. It assumes that two micelles exchange electric
charge during collision.
The disproportionation model is most widely used in Colloid Science. This field
became involved into non-polar liquid electrochemistry because amphiphilic substances,
such as surfactants, are common.
However, the disproportionation model is not the only mechanism used to describe
these phenomena. The “Fluctuation model” reflects the potential role of water in the
ionization process. The addition of water to a non-polar liquid that contains surfactant (with
a certain HLB number) leads to the formation of microemulsion droplets. Such droplets
are similar to inverse micelles to a degree, except with a water core. And similarly to
inverse micelles these droplets can exchange electric charge during collisions and become
ions. The fluctuation model theory had been derived and discussed more thoroughly in
the papers.19,20 This model can be important even when water is present in very small
amounts, as was shown in the paper.21
Lastly, the classical “dissociation model” described earlier can be extended to so-
lutions that include amphiphilic substances. The polar heads of these molecules can
occasionally dissociate like, for instance, what happens with picrate, alcohols, and ionic
surfactants. The nearby amphiphilic molecules, while still neutrally charged because they
have not dissociated, are attracted to the newly formed ions due to the dipole moment in
their polar heads.
This attraction leads to a buildup of a neutral molecule shell around each of the
charged (dissociated) ions. This, in turn, would enlarge such ions, sterically protecting
them from re-aggregation.
In electrochemical terms, the added amphiphilic substance can “solvate” ions in non-
polar liquids, which molecules have no such capacity due to their lack of dipole moments.
In contrast to aqueous electrochemistry, the added substances serve as “solvating agents”
and not necessarily as “electrolytes”. This “dissociation model with self-solvation” was
suggested in the paper.10 The term “self-solvation” is derived from the amphiphilic ion
being solvated by similar amphiphilic molecules, e.g. a dissociated ethanol ion would be
solvated by other ethanol molecules.
The structure of an ion that is “solvated with a shell of amphiphilic molecules” is
identical to the “charged inverse micelle”. In this sense “disproportionation model” and
“dissociation model with self-solvation” lead to the same result, due to the same sterically
stabilized ions.
However, there is one important difference. “Dissociation model with self-solvation”
does not require the preliminary step of neutral micelle formation. That is why it is
applicable in cases when micelles do not form such as, for instance, solutions of alcohols in
non-polar liquids.3 It can also explain ionization in a solution with surfactant concentration
below the Critical Micelle Concentration (CMC).
ORCID
Sean Parlia https://orcid.org/0000-0001-5763-0167
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