Journal of Colloid and Interface Science 531 (2018) 523–532

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Journal of Colloid and Interface Science

journal homepage: www.elsevier.com/locate/jcis

Regular Article

Adsorption of surfactant from non-polar liquid into porous material

characterized using conductivity measurement
Andrei Dukhin, Sean Parlia ⇑
Dispersion Technology Inc., 364 Adams Street, Bedford Hills, NY 10507, USA

g r a p h i c a l a b s t r a c t

a r t i c l e i n f o a b s t r a c t

Article history: Hypothesis: Surfactants cause ionization in non-polar liquids, enabling such liquids to become electrically
Received 12 June 2018 conductive with that conductivity being a linear function of the surfactant concentration. Consequently,
Revised 18 July 2018 measurement of the conductivity can be used as a tool for monitoring surfactant concentration.
Accepted 19 July 2018
Experiments: We describe here a simple method for studying surfactant adsorption from oil into a porous
Available online 20 July 2018
material. The conductivity of solutions containing toluene and porous particles was measured as a
function of time after the addition of surfactant, at various concentrations. We applied this method for
Keywords:
characterizing surfactant (SPAN 20) adsorption by porous particles (silica gel Davisil) suspended in the
Porous material
Pore size
non-polar liquid (toluene). We the suggested a simple theoretical model for the initial stage of this
Porosity adsorption process and tested its prediction experimentally.
Ion pairs Findings: The experimental data confirms all predicted theoretical trends both qualitatively and quanti-
Non-aqueous conductivity tatively. This method can be used for understanding surfactant behavior in rock formations during oil
Liquid mixtures recovery, optimizing surfactant concentration, and analyzing chemical composition.
Ions solvation Ó 2018 Elsevier Inc. All rights reserved.
Non-polar liquid
Surfactant

1. Introduction published in this Journal on the subject of surfactant’s role in oil

Surfactants are widely used these days for enhancing oil recov-
ery. They can modify the wettability of rock formations, changing
them from oil-wet to water-wet, making possible the displacement
of oil by oil/water gravity drainage. There are multiple papers
⇑ Corresponding author.
E-mail address: sparlia@dispersion.com (S. Parlia).
recovery, for example papers [1–4]. Optimization of this process
requires methods that would not only enable us to select the most
suitable surfactant for a particular rock formation based on its
composition, but also at the ideal surfactant concentration. Simply
stated, such methods should be capable of characterizing the
adsorption of surfactant by a porous material that is saturated with
either water, oil, or an oil/water mixture. It would be highly desir-
able to have such tools available in the laboratory environment for
conducting preliminary tests on a small scale.

https://doi.org/10.1016/j.jcis.2018.07.075
0021-9797/Ó 2018 Elsevier Inc. All rights reserved.
524 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532
Here we suggest such a method that, as far as we know, has not
been used for such an application. This new method is based on
measuring the conductivity of a surfactant solution in non-polar
so does this mean we can't use
liquid. non-ionic surfactants?
It has been known since late 20th century that ionic surfactants
produce stable ions in non-polar liquids, as described in the review
by Morrison [5]. The discovery of ionization in non-polar liquids by
non-ionic surfactants was made by Dukhin and Goetz in 2005 [6].
There have been many papers published on this subject since then
[7–16], which allows us to make the general statement that prac-
tically all surfactants enhance ionization in non-polar liquids, as
long as they are soluble in said liquid.
Surfactants, as well as other amphiphilic substances, serve as
solvating agents providing steric stabilization for ions in non-
polar liquids and preventing their re-aggregation into ion-pairs.
Details of this phenomenon can be found in recently published
reviews [17,18] that follow landmark works by Bjerrum, Onsager,
Fuoss, and Kraus from the early 20th century [19–23]. The corre-
sponding models of ion formation in nonpolar liquids are further
described in the Appendix A.
All of these studies revealed a linear dependence between con-
ductivity and surfactant concentration at low surfactant concentra-
tion. Some examples of these conductivity-surfactant concentration
dependences are shown in Figs. 1 and 2.
Linear dependence allows for using conductivity as a simple
measure of the surfactant concentration in a particular non-polar
liquid, including oil. In order to do this we would only need to gen-
erate a calibration curve by measuring the conductivity at a set of
known surfactant concentrations. Then we can use such calibration
curve, which would be similar to the curves in Figs. 1 and 2, to deter-
mine the surfactant concentration from the measured conductivity
for any solutions of this surfactant in the same non-polar liquid.
We apply this method here for studying adsorption of the non-
ionic surfactant SPAN 20 by porous chromatographic particles,
which serve as a convenient model for porous rock. We suspended
the particles in toluene, which models oil. We then developed a
simple theoretical model for the early stages of such adsorption
Fig. 1. Conductivity of the various non-polar liquids with SPAN 80. Abbreviation d.p stands for dielectric permittivity of the liquid, copied from the paper [6].
and verified it with experiments conducted with particles of differ-
ent sizes, porosities, and pore sizes.
1.1. Theoretical model of the initial stage that is controlled by diffusion
In this section we consider the simplest theoretical model of the
adsorption process discussed above. This model is based on several
assumptions, and the experimental setup is designed such that
these assumptions are satisfied. The experiment was conducted
on porous particles, with sizes ranging from tens to hundreds
microns, that are immersed in non-polar liquid. Intense mixing
prevents sedimentation of the particles and distributes them
homogeneously throughout the sample. Such setup allows us to
introduce following assumptions into the theory:
Assumption 1. Initial stage of surfactant penetration into the
porous particles from the non-polar liquid is controlled by
diffusion.
Assumption 2. Concentration of the surfactant [c(t)] is constant
everywhere in the liquid bulk up to the particle surface and decays
in time (t) due to irreversible surfactant adsorption inside of the
particles.
Assumption 3. Measured conductivity of the sample [K(t)] is pro-
portional to the concentration of the surfactant [c(t)] with a coeffi-
cient of proportionality [k] being independent on time:
K ðt Þ ¼ kcðtÞ ð1Þ
This assumption is based on the several experimental studies pub-
lished in the papers [6,7,15,16]. All these studies reported a linear
relationship between the measured conductivity and surfactant
concentration in the lower concentration range.
Assumption 4. Particles are monodisperse and spherical with
radius R and volume fraction in the sample u.
 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532
Fig. 2. Conductivity of the kerosene solutions with non-ionic surfactants having various HLB numbers, copied from the paper [6].
Assumption 5. Pores have radius [a] with total porosity P. We also
assume the simplest geometry of pores making their length equal
to the diameter of the particle (2R), as well as being straight and
open on both ends.
Assumption 6. The non-polar liquid saturates and wets the porous
space inside of the porous particles. In order to assure this assump-
tion we add surfactant to the liquid prior to the adding particles.
The surfactant promotes wetting of the pore walls and ensures sat-
uration of the pores with the non-polar liquid.
The theoretical model that we are looking for should yield an
equation describing the evolution of measured conductivity over
time. These kinetics would reflect depletion of the surfactant in
the bulk liquid due to its adsorption by the porous particles. An
equation for the total surfactant amount preserved in the bulk [c
(t)] is the starting point for such mathematical model. It can be
written as the following:
Z dcðtÞ
t
V ½c0  cðtÞ ¼ J ðt Þdt ð2Þ
0
where V is the total sample volume, c0 is the initial concentration of
the surfactant, and J(t) is the diffusional flux of the surfactant from
the liquid bulk into the porous particles.
This diffusional flux can be linked to the surfactant concentra-
tion with the following equation:
dcðt; rÞ
J ðtÞ ¼ D S ð3Þ
dr r¼R
where c(t,r) is concentration of surfactant at time t and distance r
from the particle center inside of the pores, D is the diffusion coef-
ficient of the surfactant molecules, and S is an area of the cross-
section that is open for surfactant molecules to diffuse inside the
particles.
Concentration of the surfactant diminishes from the bulk into
the particles, which requires a minus sign () in front of the special
derivative. We do not know the value of the concentration gradient
525
in general. But, we can introduce a simple assumption that should
be valid for short times during the initial stage of diffusion.
Assumption 7. Diffusional flux at the early stages of this process
occurs mostly at the entrance of the pores, since surfactant that
enters the pores will be completely adsorbed in the vicinity of the
entrance. We can assume that the concentration of the surfactant
drops from c(t) at the very entrance of the pore down to 0 over
certain distance D. We assume that this distance D remains
constant and is time independent during early stages of adsorp-
tion. This leads to the following approximate equation for the
diffusional flux:
cðtÞ
J ðt Þ ¼ D S ð4Þ
D
Substituting this equation into Eq. (2) and applying the time
derivative leads to the following differential equation for c(t):
DScðtÞ
V ¼ ð5Þ
dt D
Solving this simple differential equation yields following
expression for c(t)
cðtÞ DS
ln ¼ t ð6Þ
c0 VD
We can link the diffusion cross-sectional area per unit volume
(S/V) to the geometric properties of particles using Assumptions
4 and 5.
The total diffusion cross-section for a single particle (Sp) is equal
to the product of the pore cross-sectional area (pa2) and the num-
ber of the pores Np:
Sp ¼ Np pa2 ð7Þ
The number of pores can be expressed by using the definition of
the porous material’s porosity P as the ratio of the pore volume
(Np * pa2 * 2R) to the total volume of the particle (4/3pR3). This
leads to the following expression for the number of pores in a sin-
gle particle:
526 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532

2 R2 the same 60 Å pore size but different particle sizes, as shown in

Np ¼ P ð8Þ Table 1. The other two types of the particles have a pore size of
3 a2
150 Å and different particle sizes, as also shown in Table 1.
Substituting this expression for Np into Eq. (7) leads to the fol-
Table 1 specifies the particle size ranges for the each material
lowing equation for the diffusional cross-section of a single particle:
type in mesh size as is given by Sigma-Aldridge, and in microns
2 as converted by us.
Sp ¼ pPR2 ð9Þ
3 There is no information given for the median particle size. We
The total number of particles Nv in the sample volume V can be were able to measure median particle size using a Dispersion Tech-
expressed as a function of the porous material volume fraction u: nology DT-100 Acoustic spectrometer that functions in accordance
with ISO standard ISO-20998 [24]. It is described briefly below. The
3V u measured particle size values are also shown in Table 1.
Nv ¼ ð10Þ
4pR3 The manufacturer has not reported the porosity values for these
Finally, the total diffusion cross-section equals the diffusion particles. We measured the porosity using a Dispersion Technology
cross-section for a single particle multiplied by the number of DT-900 Porosity Meter, which is described below. Values of poros-
particles: ity are reported in Table 1.
We used the non-ionic surfactant SPAN 20 (Sorbitan Monolau-
uPV rate) purchased from Sigma-Aldrich in these experiments. This sur-
S¼ ð11Þ
2R factant has the following properties: density is equal to 1.032 g/cc,
Substituting this equation into Eq. (6) leads to the following and the HLB number is 8.6. The rather high HLB number ensures a
simple expression describing the initial stage of surfactant concen- substantial conductivity increase will occur when this surfactant is
tration evolution: added to the non-polar liquid.
The non-polar liquid used in these experiments was Toluene.
cðtÞ DuP
ln ¼ t ð12Þ Pure (99.9%) toluene was purchased from Sigma Aldrich.
c0 2RD
Finally, we can apply Assumption 3 in order to link surfactant 2.1. Sample preparation and measurement procedure
concentration to the conductivity, which is measurable parameter.
This leads to the following expression, which is supposed to reflect The first step in the sample preparation was to mix the non-
the initial stage of conductivity evolution due to surfactant adsorp- ionic surfactant SPAN 20 with toluene. We added 1 g of SPAN 20
tion in the porous particles: into 49 g of toluene, yielding a concentration of 2% by weight. This
KðtÞ DuP liquid mixture was prepared in a cup with a diameter sufficiently
ln ¼ t ð13Þ small enough to allow the conductivity probe to be inserted into
K0 2RD
the cup, while minimizing evaporation of the liquid. The small
There are several theoretical predictions that can be derived diameter also ensures that the liquid reaches a sufficiently high
regarding the evolution of conductivity normalized with the con- level such that both electrodes of the conductivity probe
ductivity of the pure surfactant solution: (described in the next section) are covered.
KðtÞ This cup is placed on magnetic mixing plate with a small mag-
K¼ ð14Þ netic cross in the bottom of the cup. The rate of mixing generated
K0
by the rotating magnetic cross is very important. It must be high
Prediction 1. The logarithm of the normalized conductivity is a enough to keep the porous particles suspended in the liquid.
linear function of time at the early stages of the described The second important function of mixing is supporting Assump-
adsorption process; tions 1 and 2 of the suggested theoretical model, which state that
Prediction 2. The rate of this linear time dependence is recipro- the surfactant concentration is constant everywhere in the liquid
cally proportional to the particles size; bulk, and that the adsorption process is controlled by diffusion of
Prediction 3. The rate of this linear time dependence is propor- the surfactant into the particles.
tional to the porosity of the particles; We have verified these assumptions by conducting measure-
Prediction 4. The rate of this linear time dependence is propor- ments at several rates of magnetic cross rotation and showing that
tional to the volume fraction of the particles. the conductivity in the presence of porous particles is independent
Prediction 5. The rate of this time dependence is independent of the rotation rate in the range that we used.
on pore size. This is the most surprising and counterintuitive Continuous measurements of conductivity begin with the
prediction. toluene-surfactant mixture without any porous particles present.
We can verify all these theoretical predictions via experiment, This allows us to verify that the initial concentration of surfactant
which is the main purpose of this paper. (and hence the conductivity) is the same for all samples.
We then add 1 g of porous particles into the cup with toluene-
2. Materials and sample preparation surfactant mixture without interrupting the ongoing conductivity
measurements.
We used 5 different types of silica gel Davisil porous particles Conductivity of the sample begins to decay in time due to
purchased from Sigma-Aldrich. Three types of these particles had surfactant adsorption by the particles. The rate of this decay

Table 1
Properties of silica gel porous particles Davisil. Source of information: * - manufacturer, ** - acoustic particle sizing [24], *** - high frequency conductivity [23].

Name Pore size, Angstrom* Particle size, mesh* Particle size, micron* Particle size d50, micron** Porosity, %***
Davisil 633 60 200–425 30–75 45.8 45.95
Davisil 635 60 60–100 150–250 247.0 43.83
Davisil 636 60 35–60 250–500 345.0 47.02
Davisil 643 150 200–425 30–75 72.6 64.08
Davisil 646 150 35–60 250–500 397.0 60.35
 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532
slows with time. We kept the measurements going until the con-
ductivity reaches saturation and remains practically unchanged
with time.
2.2. Instruments
We used 3 different instruments for measuring conductivity,
porosity, and particle size.
2.2.1. Conductivity measurement
A DT-700 non-aqueous conductivity probe made by Dispersion
Technology, Inc. was used for measuring conductivity in these
experiments The DT-700 is able to measure from 10E11 to
10E4 S/m, with a single-measurement precision of ±(1% +
10E11 S/m) over the complete range. By taking multiple mea-
surements for a single data point, this precision is improved.
The DT-700 probe consists of two concentric coaxial cylindrical
electrodes: an inner one and an outer one, along with a guard elec-
trode which serves to prevent leakage. In order to make a measure-
ment, the probe is dipped into the sample such that the holes in
the outer electrode are covered. This outer electrode can also be
removed for cleaning.
The newest model of the DT-700 measures current using a log-
amplifier which requires no ‘‘range selection.” A voltage waveform
is applied to the outer electrode, while the output signal from the
log amplifier is simultaneously captured by second channel of the
Analog-to-Digital converter. The desired waveform is then calcu-
lated from the captured log-amp values through an inverse log cal-
culation. This technique still allows for measurements to be made
over many decades of current.
First order Fourier coefficients are used to calculate the ampli-
tude and phase of both the voltage and current waveforms. The
Complex Conductance of the cell contents is then computed from
the current voltage ratio. Lastly, the specific conductivity of the
sample material is determined by computing the real part of the
complex conductance and then multiplying by a cell constant,
which is determined via instrument calibration.
Fig. 3. Conductivity evolution of toluene-Span 20 mixtures with 2% wt porous silica gel Davisil 646. Span 20 was added twice (1 g each) to the mixture after conductivity
reaches saturation.
527
2.2.2. Porosity measurement
Porosity measurements were conducted with a Dispersion
Technology DT-900 Porosity Meter. This instrument applies a high
frequency 3 MHz electric field for measuring porosity of porous
materials. This instrument is described in detail in the paper [25].
2.2.3. Particle size measurement
Particle size distribution of the porous particle dispersions was
measured with a Dispersion Technology DT-100 Acoustic spec-
trometer (for details, see the recently published book [26]). This
method is done by measuring the attenuation of ultrasound prop-
agating through the sample as a function of frequency, from 1 to
100 MHz. Then, a theoretical fit is used for finding a particle size
distribution that produces a theoretical attenuation frequency
spectrum that matches the experimental one with the least error.
There is a very useful simplification of the particle size search for
sizes exceeding 10 mm where the particles scatter ultrasound. This
simple algorithm indicates that the median particle size is approx-
imately 2/3 of the wavelength at the frequency corresponding to
the maximum scattering attenuation, expressed in units of dB/
cm/MHz. All samples studied in this paper have particle sizes much
larger than 10 mm, which allowed us to use this simple method for
estimating the median particle size. The results are shown in
Table 1.
3. Experimental results and discussion
Fig. 3 presents the evolution of measured conductivity over
time for one type of porous particle – silica gel Davisil 646. The
conductivity decays over time because the porous particles adsorb
surfactant. The concentration of surfactant in the bulk toluene
declines, which leads in turn to the drop in conductivity.
The rate of conductivity decline slows down over time because
the diffusion flux decreases with diminishing bulk surfactant con-
centration. Eventually, equilibrium between the bulk and the por-
ous particles’ interior is established and the conductivity reaches
saturation.
528 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532

Fig. 4. Reproducibility test. Evolution of toluene-Span 20 mixtures with 2% wt porous silica gel Davisil 646, 2 repeated measurements.

Fig. 3 demonstrates that addition of the surfactant at this satu-
ration stage would lead to a sharp increase in the conductivity,
with a second step of the conductivity slow declining to follow.
It is interesting that the second saturation level exceeds the first
one. This reflects the process of the pores gradually filling up with
surfactant.
The third addition of surfactant, as shown in Fig. 3, causes only a
very small increase in conductivity, because the pores have appar-
ently already been almost filled.
We have decided to use the only the first leg of this equilibra-
tion kinetics for testing the primitive theoretical model for this
process suggested above. Fig. 4 demonstrates that we can repro-
duce this first leg quite precisely.
Fig. 5 presents conductivity evolution data for all 5 types of the
porous particles that we studied. In order to make the differences
between these curves more pronounced, and to compare this
experimental data with the theoretical predictions, we converted
this figure to another one, Fig. 6, which presents the logarithm of

Fig. 5. Conductivity evolution of toluene-Span 20 mixtures with 2% wt of various porous silica gel Davisil particles.
 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532
Fig. 6. Evolution of ln(K(t)/K0) over time for dispersion of various porous silica gel Davisil particles at 2% wt in toluene-2% SPAN 20 mixture. Solid lines and equations
correspond to theoretical best linear fit according to Eq. (13).
the so-called ‘‘normalized conductivity”, ln(K(t)/K0). The theory
yields the following expression for this parameter, first described
in Eq. (13):
KðtÞ DuP
ln ¼ t ¼ At
K0 2RD
The coefficient A on the right hand side of this equation can be
considered as the ‘‘rate of conductivity decline”. We will use this
term below for the fitting parameter of the linear regression to
the experimental data.
There have been several theoretical predictions made for this
parameter in Section 2. We can verify all of them using the curves
shown in Fig. 6, and confirm that these experimental curves con-
firm all theoretical prediction qualitatively.
Prediction 1. All experimental curves in Fig. 6 exhibit a linear
dependence of the logarithm of the normalized conductivity
on time, as predicted with Eq. (13) at the initial stages of the
adsorption process. This linearity is especially pronounced for
the 3 samples with larger sizes: Davisil 635, 636 and 646.
Prediction 2. The rate of this linear time dependence A indeed
increases with decreasing particle size. The fastest conductivity
decline is for the samples with sizes ranging from 30 to 75 mm.
The sample with sizes ranging from 150 to 250 mm is the next
fastest, and the samples with the sizes of 250–500 mm demon-
strate the slowest decline.
Prediction 3. The rate of this time dependence A increases with
porosity. Samples 646 and 636 have the same particle size
range of 250–500 mm. However, sample 646 has a higher poros-
ity of 60% compared to the sample 636 which has a porosity of
45%. The rate of conductivity decline for sample 646 is much
higher than for sample 636.
However, the difference in the rates between samples 646 and
636 cannot be explained just by porosity differences. The porosity
ratio between these two samples is about 4/3, whereas ratio of the
linear regression coefficient for these two curves is 0.3515/0.1549
529
(7/3). The experimental ratio is much bigger than the theory
predicts.
We suspect that this discrepancy is the result of particle size
differences between the samples. If the particle size of sample
646 is somewhat smaller than for sample 636, this could reconcile
the ratio of theoretical and experimental rates.
This observation points towards importance of detailed particle
size information for interpreting these experiments.
Prediction 4. The theory predicts that the rate must be propor-
tional to volume fraction of the particles.
We have conducted a special test for verifying this prediction
by measuring the decrease in conductivity over time for samples
with different particle concentrations: 0.5 g, 1 g, and 2 g in 50 ml
of the toluene-surfactant mixture. We have done this for the
sample 636, which has the largest pore size and largest particle
size.
The results are shown in Fig. 7. Each volume fraction was mea-
sured twice in order to ensure reproducibility. It can be seen that
these measurements are in fact very reproducible.
The theory predicts that the rates for these samples with differ-
ent volume fractions should vary as a ratio of volume fractions,
meaning 0.5:1:2. The rate of the most diluted sample (with 0.5 g
of particles) must therefore be 4 times slower than the rater for
the most concentrated sample (with 2 g of particles).
The experimental results demonstrate a much different ratio
surprisingly. The ratio of the averaged linear regression coefficients
shown in Fig. 6 are 0.095:0.31:1.57.
This means that the ratio of the slowest rate to the fastest rate is
16.5.
This means that the experiment points towards a square depen-
dence of the conductivity decline rate, instead of the theoretical
linear dependence shown in Eq. (13).
We have no explanation for this difference as of now. Particle
size cannot be the reason because this anomaly is observed for
samples with the same size particles.
530 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532
Fig. 7. Volume fraction dependence test. Evolution of ln(K(t)/K0) over time for dispersion of Davisil 646. Particle content varied as 0.5 g, 1.0 g and 2.0 g in 50 ml of the toluene-
surfactant solution. Each sample was measured 2 times. Solid lines and equations correspond to theoretical best linear fit according to Eq. (13).
Prediction 5. The rate of this time dependence is independent
on the pore size. This is the most surprising and counterintu-
itive prediction. However, the experiment confirms this conclu-
sion. It turns out that we can reconcile the rates of adsorption
for different samples quantitatively using just particle size
and porosity data. This is shown in the next sub-section.
3.1. Comparison of the adsorption rates quantitatively
According to Eq. (13), the rate of adsorption at the early stages
of this process is defined in the theory as:
DuP
A¼
2RD
We cannot calculate this parameter because we do not know
the values of the diffusion coefficient D and diffusion distance D:
However, we can compare the rates for different samples since
the ratio of these rates would depend on the particle size and
porosity only. For instance, the ratio of rates for the two samples
with the smaller sizes, samples 633 and 643, is equal to:
DuP 633
A633 2R633 D P633 R643
theory : ¼ ¼
A643 D2RuP643D P643 R633
643
Substituting in the values of porosity and particle size for these
two samples (from Table 1) leads to the following theoretical value
for the adsorption rate ratio for these two samples:
A633
theory : ¼ 1:14
A643
On the other hand, we can calculate the ratio of rates from the
linear regression coefficients shown in Fig. 6:
A633 5:8211
experiment : ¼ ¼ 0:88
A643 5:1236
There is a difference between the theoretical value of the ratio
of the rates (1.14) and the experimental value (0.88), but it is much
smaller than the difference in pore sizes between these two
samples (2.5 times). The most likely origin of this difference
between theory and experiment is uncertainty of the particle size.
Unfortunately, uncertainty in particle size increases for samples
with larger sizes. Consequently, we may expect an increase in the
deviation between theory and experiment for the samples with
larger particle sizes.
The ratio of the rates for the samples with largest sizes (636 and
646) are 0.89 for the theory and 0.44 for the experiment, which is
still much less than pore size differences.
The ratio of the rates for the samples with the intermediate size
(635) and the smallest size (633) are 0.185 for the theory and 0.104
for the experiment, which is still much less than pore size
ð14Þ differences.
We believe in general that the simple theory suggested above
provides a surprisingly close fit to the experimental data, even
on a quantitative scale.
4. Conclusions
This study stresses the ability to study the adsorption of surfac-
tant into the pores of porous materials via conductivity measure-
ð15Þ
ments of the bulk nonpolar liquid said porous material is
saturated with. We proposed a simple theoretical model to
describe such systems and their change in conductivity over time
as this adsorption occurs. Our model implied that the logarithm
of the normalized conductivity is a linear function of time (at early
the adsorption stage).
ð16Þ From this model we made predictions about how other param-
eters – particle size, porosity, volume fraction of particles, etc. –
impacted this linear time dependence. Most interestingly we pre-
dicted that this linear time dependence was independent of pore
size.
ð17Þ By studying non-polar systems in which non-ionic surfactant
SPAN 20 was added to mixtures of toluene and non-conducting
porous particles, we were able to confirm each of the predictions
we made in this paper. This includes confirming that conductivity
trends were independent of pore size for a given particle.
 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532
We have shown first that overall bulk conductivity will
decrease as a function of surfactant adsorption, and that this trend
can be repeated by adding additional surfactant to the nonpolar
continuous phase (see Fig. 3). We have also demonstrated that
not only is there a linear dependence of conductivity on surfactant
content at low concentrations, but also that there exists a linear
time dependence on the adsorption of surfactant into porous mate-
rials during the initial adsorption stage. It is from this initial linear
adsorption rate that the model was derived for examining the driv-
ing factors in this adsorption process.
We measured suspensions of porous particles that varied in
concentration, particle size, and pore size. We were able to estab-
lish trends that were consistent across both theoretical and exper-
imental data, and are confident that this technique can be used to
further understand and predict the adsorption of surfactant by por-
ous materials. However, while the trends we predicted were con-
firmed experimentally, their actual rates deviated from the
predicted values. We suspect that these discrepancies are due to
discrepancies in particle size distribution. And while we did mea-
sure the particle size of these porous particles using acoustic spec-
troscopy, we were unable to resolve these differences using this
technique alone. A more rigorous examination into the particle size
distribution of these porous particles would be useful for upcom-
ing research in this field.
Lastly, this research was initiated by studies conducted in 2005
by Dukhin and Goetz [6] pertaining to the of ionization of non-
polar liquids via non-ionic surfactants. Parlia and Dukhin contin-
ued this work, publishing several additional papers on nonpolar
liquids’ electrochemistry [12,13,15,17]. Furthermore, it was shown
that other amphiphilic substances such as alcohols can also induce
ionization of nonpolar liquids [14]. We have now expanded upon
this work to include porous materials saturated with ionized
non-polar liquids, and developed a theoretical model with which
to better study such systems.
Appendix A. Models of ion formation in non-polar liquids
There are two recently published reviews [17,18] on the elec-
trochemistry 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 are in consensus with pre-
vious studies of non-aqueous electrochemistry conducted in early
20th century by Bjerrum, Onsager, and Fuoss [19–23]. They con-
clude that the balance between free ions and ion-pairs is a control-
ling 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 dielectric constant 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 [21–23]. 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 ion-
ization. There is practically no discussion about the state of the
small counter-ions that split from the large picrate molecules.
531
The fact that these ions cannot be solvated by the non-polar liquid
molecules due to lack of the 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) publica-
tions [27].
This model ignores the existence of 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 and 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 [28]. In that paper they wrote that
‘‘. . .in a non-polar solvent, aggregation is clearly the result of a bal-
ance between the solubilizing power of the hydrocarbon chains
and the attractive forces between polar parts of the soap [surfac-
tant] 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 added molecular dipoles
would affect the formation of ions in non-polar liquids.
According to Morrison [5], a paper by Mattoon and Mathews
from 1949 [29] 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 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 electro-
chemistry because amphiphilic substances, such as surfactants,
are common.
However, the disproportionation model is not the only mecha-
nism 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 microemul-
sion 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 [30,31]. This model can
be important even when water is present in very small amounts,
as was shown in the paper [32].
Lastly, the classical ‘‘dissociation model” described earlier can
be extended to solutions that include amphiphilic substances.
The polar heads of these molecules can occasionally dissociate like,
for instance, what happens with picrate, alcohols, and ionic surfac-
tants. 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.
532 A. Dukhin, S. Parlia / Journal of Colloid and Interface Science 531 (2018) 523–532
In electrochemical terms, the added amphiphilic substance can
‘‘solvate” ions in non-polar liquids with molecules having no such
capacity due to their lack of dipole moments. In contrast to aque-
ous electrochemistry, the added substances serve as ‘‘solvating
agents” and not necessarily as ‘‘electrolytes”. This ‘‘dissociation
model with self-solvation” was suggested in the paper [17]. The
term ‘‘self-solvation” is derived from the amphiphilic ion being sol-
vated 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 amphi-
philic 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 ster-
ically 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 alco-
hols in non-polar liquids [12]. It can also explain ionization in a
solution with surfactant concentration below the Critical Micelle
Concentration (CMC).
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