Novel Conductivity-Enhancing Ionic

Surfactants in Nonpolar Liquid

Submitted in partial fulfillment of the requirements for the degree of Master

of Science Chemical Engineering and
Colloids, Polymers, and Surfaces

Sixue Cheng
B.S., Applied Chemistry, South China University of Technology
M.S., Chemical Engineering, Carnegie Mellon University

Carnegie Mellon University Pittsburgh, PA

December 2014

Acknowledgement
I would like to use this opportunity to express my gratitude to everyone for the
positive impact on my Master study. I am thankful for their guidance, aspiring,
constructive criticism and friendly advice during my Master project work. For starters,
I would like to thank my advisor Professor Dennis Prieve and my co-advisor
Professor James Schneider. Throughout my whole project, you always give me so
much helpful suggestion and you are always being so inspiring. You two wonderful
advisors taught me a lot in this project, not just academic knowledge but also the
correct attitude toward research, which will inspire me in my future study and career.
Im sincerely appreciating the support from my colleagues and fellow graduate
students, Xiaoyu Liang, Yuan Fang, Ben Yezer and John Goldman. Ben Yezer and
John Goldman, thank you for your numerous technical supports during me experiment
and helping me place the orders. Xiaoyu Liang, thank you for your DLS data and
Mass Spectrometry result, and thank you for every constructive discussion we had.
Yuan Fang, thank you for your dye solubility data and your other supporting data.
I would also like to thank Professor Sides and Professor Khair, who provide a lot of
constructive suggestion on our weekly group meeting.
Finally, I would like to appreciate my parents who sponsor my Master education in
the United State.

Abstract
Surfactants are not only widely used in aqueous systems as detergent, wetting agents
and dispersants, but also act as a conductivity- enhancing agent in nonpolar system.
Researches show that both ionic surfactant and nonionic surfactant could efficiently
increase the nonpolar liquids conductivity when added. This phenomenon is due to
reversed micelle structure formed in the nonpolar media, which the reversed micelle
acting as a charge carrier. This process has a very wide application, like in petroleum
handling, drug delivery, printer inks and electrophoretic display used in E-books.
Thus, the nature of surfactant charging process in nonpolar media has gained much
attention recently.
Previous works show that, the conductivity enhancement ability is related to varied
surfactant molecular properties: molecular structure and counter ion. In this research,
to better understand how these properties affect the charging process and the charging
mechanism, couple similar surfactants are synthesized: (1) Asp-(C8b)2-(pTs); (2)
Asp-(C12b)2-(pTs); (3) Asp-(C8b)2-(SO4); (4) Unbranched Variant. Those self-made
surfactants are compared with 2 similar surfactants: AOT; and a nonionic surfactant
sample from Dow company, the differences among them show on charging functional
group, length of tail and counter ion.
The conductivity and micellar size is determined for those surfactants solution in
dodecane. The result shows, there are a certain relationship among micellar size,
conductivity enhancement ability, functional group and tail length. And among those
surfactants, Asp-(C8b)2-(pTs), which is considered as a mixture of nonionic
surfactant and ionic surfactant, shows a greater exponent of 2 in conductivityconcentration log-log function than other surfactant, which only around 1.2. Possible
explanations are provided for this behavior.

ii

Table of Contents
Acknowledgement-..............................................................................................................-i!
Abstract-.................................................................................................................................-ii!
Table-of-Contents-.............................................................................................................-iii!
1.-Introduction-....................................................................................................................-1!
2.-Materials-and-Method-..................................................................................................-5!
2.1-Materials-Synthesis-..............................................................................................................-5!
2.1.1!Asp((C8b)2((pTs)!...........................................................................................................................!6!
2.1.2!Asp((C12b)2((pTs)!........................................................................................................................!7!
2.1.3!Unbranched!Variants!....................................................................................................................!8!
2.1.4!Dow!free!amine!Surfactant!and!Asp((C8b)2((SO4)!..........................................................!9!
2.2-Purification-.........................................................................................................................-10!

3.-Experimental-Result-..................................................................................................-10!
3.1-Purification-and-Composition Analysis-........................................................................-11!
3.1.1!Purification:!CombiFlash!Solvent!.........................................................................................!11!
3.1.2!Purification!Peak!Analysis!and!Mass!Spectrometry!Result!.......................................!13!
3.2-Solubility-of-Surfactant-....................................................................................................-16!
3.3-Conductivity-and-Micellar-Aggregation-.....................................................................-17!
3.3.1!Conductivity!...................................................................................................................................!17!
3.3.2!Micellar!Aggregation!Analysis!...............................................................................................!24!

4.-Discussion-.....................................................................................................................-25!
5.-Conclusion-....................................................................................................................-28!
6.-Reference-......................................................................................................................-29!

iii

1. Introduction
Surfactants are a kind of compounds that lower the surface tension between two
liquids or between a liquid and a solid, acting as a surface-active agent. Surfactants
are usually organic compounds that are amphiphilic, containing a hydrophilic group
the head and a hydrophobic group the tail. This special structure allows it forming a
micelle structure in both aqueous and nonaqueous liquid (reversed micelle) when
surfactants molecule is concentrated enough in solution. In the case where an
aqueous solution of surfactant is mixed with a nonpolar liquid, surfactant will adsorb
at the interface: the hydrophobic tail will extend into the nonpolar phase and
aggregate together while the hydrophilic head group remains in the aqueous phase,
forming a micelle structure. Because of the micelle structure, the surfactant solution
above a certain concentration (critical micelle concentration), the solutions properties
may act very differently than without surfactant.
Since its so useful to manufacturing, surfactants in aqueous solution have been
widely studied and well understood in the past. Since about the 1950s, an interest has
risen in detergents in nonpolar solutions, more and more attention is focused on the
properties and applications of reversed micelles which are formed by surfactants
dissolved in nonpolar media. In aqueous environments, surface charge on colloidal
particles is very common and causes electrostatic stabilization of the colloidal
particles. Nonpolar solutions are considered to be charge free because of the large
energy needed to separate positive from negative charges. However, charging in
nonpolar media does occur and was first report in 1950s[1,2], the conductivity of
nonpolar media has even a much older history dating back to the 1890s[24]. Research
also show that the charge carrying species is the reversed micelle formed when
surfactants are dissolved in nonpolar media[3]. To understand this charging
phenomena and control this process is a very significant topic which could be applied
in area like petroleum industry, for stabilizing colloidal dispersions, preventing
explosions[4,5], drug delivery[6], printer inks and electrophoretic display used in Ebooks[7].
1

How surfactant controls the charges in nonpolar solvent have been studied for years,
In 1993, Morrision[8] reviewed the electrical charge phenomena in nonpolar media
and display the research about ions stabilization in non polar liquid, reversed
micelles formation, conductivity enhancement and other related topics at that time.
This review is very helpful to understand the basic theory about charging process in
nonpolar media. Later, more research focused on controlling the charging process in
nonpolar liquid with surfactant, like ionic surfactants AOT is studied in nonpolar
media dodecane that by below CMC and above CMC by attached with particle
PMMA: when above CMC, there is little surface charge on particle while in
submicelle area, the solutions conductivity () shows ~ C1/2 and micelle regime of
~ C [8,9]. Nonionic surfactants like PIBS and sorbitan ester of the span family, which
without ionic group have been also studied and identified as a powerful charge control
agents[10,11]. Some excellent reviews report recent studies about how ionic surfactant
and nonionic surfactant control charge stabilization [12, 13].
To better understand how charge process is performing in nonpolar media, we first
introduce a concept of the Bjerrum length. The Bjerrum length B is the distance
between two point charges (both equal to +/- e) at which the electrostatic potential
energy equals the thermal energy kT, B =

e2
, where 0 is vacuum
4 0r kBT

permittivity; r is relative permittivity; e is the elementary charge. If we treat an ion

pair as two point charges (having opposite sign), then the center-to-center distance
when they are associated might be compared to the Bjerrum length. If the distance is
larger than the Bjerrum length, then the ion pair might dissociate as a result of thermal
agitation to form charge carriers. If the distance is smaller than the Bjerrum length,
then the ion pair is unlikely to dissociate and no carriers will be formed. For polar
media like water at room temperature, r = 80 and B = 70nm .
Research shows that the charging process in nonpolar media is much more difficult
than aqueous solution due to the lower r[3] and consequently larger

which means

that the charges in non-polar solvent need to be separated by a larger distance to carry
2

charge, such as they are in large enough sizes, or are carried by a large enough
structure like polymer or micellar structure. For example, in dodecane, because of the
relatively larger r, 28nm is needed to keep charge stable, while in water

is only

0.79nm. In nonpolar media, its hard to keep ion stable, and micelle structure offer a
suitable environment to keep a large

.So its reasonable that when above CMC and

surfactant molecules start forming micelle or pre-micelle structure, the solutions

overall conductivity will increasing because ion could stably exist in this environment.
For some kind of surfactant, instead of micelle or pre-micelle, they form oligomer
because of comparatively large r and head group radii d, which aggregation number
depends on surfactant concentration[14]. Previous research shows it may also increase
solutions conductivity [15].
From the surfactant forming reversed micelle structure in nonpolar solution, the
disproportionation mechanism[10] is a very well-accepted theory that how micelles
charging in nonpolar media: two neutral inverse micelles exchange charges, forming
two micelle with contrary charge, one negative and one positive. Karvars work report
that[16], if we assume the aggregation number is constant, then the conductivity is
proportional to the surfactant concentration .
So far, previous works show a theory about how charging process occurred in
nonpolar media, however, the comprehensive phenomena remains elusive and there is
still some mystery need to be explored. This study focuses on how the surfactants
properties, like structure, counter ion and surfactants electrical polarity affect
charging stabilization. To conduct this, since commercial surfactant AOT is widely
studied in nonpolar solvent, we plan to synthesize a series AOT like surfactants,
varying the hydrophobic tails structure and the hydrophilic heads electrical polarity.
Then make a series of concentration solution of this surfactant and nonpolar solvent
dodecane, measuring the solutions conductivity. The conductivity measurement is a
common method to study the electrical charge carrying species. Research shows when
surfactant is added in nonpolar liquid, because of the charging process occurred on
micelles interface, it would efficiently enhance the solutions conductivity. Therefore,
by studying the conductivitys enhancing ability of certain surfactant, we a further
3

realized how the electrical stabilization is carried out by the surfactant. Furthermore,
DLS and dye solubility measurement is also applied to study the micelle size and
critical micelle concentration (CMC), which help us to understand surfactants
micellar properties

2. Materials and Method

2.1 Materials Synthesis
We synthesized a series of surfactants which share a similar structure with the
commercial surfactant Aerosol OT (AOT, Sodium di-2-ethylhexyl-sulfosuccinate ).
We decided to choose AOT as prototype because it has a good stabilizing and
charging properties when it is added into nonpolar media like dodecane. Furthermore,
the nonpolar solvent - surfactant (AOT) system is well studied recently. Thus, we
believe, by studying different kind of surfactants, which are similar to AOT could
help us understand how a surfactants structure could affect the charging property of
nonpolar media- surfactant system. Then, explore the mechanism of electrostatic
stabilization in Nonpolar Media.
CH3
+

Na O

CH3

The surfactant we synthesize to compared with AOT

counter ion. However, to keep the surfactants

O
O
CH3
AOT's Structure

are slightly different both in the tail structure and

solubility and charging properties similar to AOT, we

CH3

didnt change too much on the main structure. And the

AOT homologues can be divided into three types:

altering the tail; altering the counter ion; altering both the tails and the counter ion.
Even though the structure and synthesis schemes are similar, the product obtained
may have different properties which will be discussed in the next chapter. The
homologues structure and synthesis scheme is explained in this part.
To synthesize a series of homologues structure like AOT, we use the reaction
scheme similar to that for AOT which is cited from Asakuma et al[17] and Baczko et
al[18] and then use the Combiflash Chromatography to purify the product. All these
reactions go through a Fischer-Speoer esterification.

Scheme 1. Fischer

Speier esterification[19]

2.1.1 Asp-(C8b)2-(pTs)
1,4-bis((2-ethylhexyl)oxy)-1,4-dioxobutan-2-aminium-methyl-benzenesulfonate
( Asp-(C8b)2-(pTs)) is synthesized in this part. The reactions are showed as Scheme 2.

(1). Add Toluene as solvent and heated for about 5 to

6

hours.

The

two

tails

are

attached

to

headgroup( aspartic acid).

(2). Purify it with ComboFlash, the pTs counter ion is
removed, leaving a free amine part (and some Asp(Cb8)2-pTs)

Scheme 2
6

30

ml

(192mmole)

2-ethylhexanol

12.77(96mmole) Aspartic acid (

(99%,

Sigma-Aldrich

Corporation),

99% , Sigma-Aldrich Corporation), 20.06g (106

mmole) p-Toluenesulfonic acid (pTs, 99%, ACROS

ORGANIC Corporation) and 600ml toluene (99%, EMD
Millipore) as solvent are combined ( no reacted). All of
these are added into a 1000ml round flask and be placed
in a Dean-Stark apparatus (figure 1.) to monitor and
remove the water produced by the reaction. The
collection water is about 5.3 ml, which is predicted by
stoichiometry, after reaction time of 5 hours. After that,
the toluene will be evaporated by rotor evaporation, and
Figure 1

the

residue

purified

using

the

Combiflash

Chromatography (CombiFlash Rf 200i, TELEVYME ISCO). Then a clear, viscous,

colorless product is obtained, which should be a mixture of the free amine and real
Asp-(C8b)2-pTs, but for convenience, we just denote as Asp-(C8b)2-(pTs) where
the parentheses around pTs indicating the synthesis method .
Asp-(C8b)2-(pTs) has the same tail as AOT, the only difference is the charge
carried by head group: For AOT, the head group carries a positive charge, it is a
cationic surfactant ; And Asp-(C8b)2-(pTs), before Combiflash, its head group carry
negative charge(Asp-(C8b)2-(pTs)); After purification, the pTs are removed from
some molecules head group, then the product is the mixture of free amine and
ionic, called Asp-(C8b)2-(pTs).

2.1.2 Asp-(C12b)2-(pTs)
1,4-bis((2-butyloctyl)oxy)- 1,4-dioxobutane-2-ammonium-methyl benzenesulfonate
(Asp-(C12b)2-(pTs)) is obtained through a same reactio. The same mole chemical
materials (from the same company as 2.1.1) are added in 1000 ml round flask and
heated until 5ml water is collected. Compared with Asp-(C8b)2-(pTs), this one need
longer time to reaction because of stronger steric hindrance. The total reaction time is
7

about 9 hours with 5ml water collection.

Similar with Asp-(C8b)2-(pTs), this product is also a mixture of free amine and
ionic surfactant. The difference from Asp-(C8b)2-(pTs) is the tail for Asp-(C12b)2(pTs) is longer by 2 carbon, both for main chain and branch.
CH3

CH3

CH3

O
O S

CH3

O H3N

H2N

O
O

CH3

CH3

H3C

CH3

H3C

Figure 2. Asp-(C12b)2-pTs with counter ion and without counter ion( free amine)

2.1.3 Unbranched Variants

In this part, we also try to synthesis a series of surfactants that dont have any
branched structure on their tail by the same scheme. The structures are shown in
Table 2 (the structure shown is the free amine):
Name
(tail name and source)

Structure
O

Asp-(C6)2-Pts

H2N

(1-Hexanol
reagent grade, 98%, Sigma-Aldrich)

CH3

CH3

Asp-(C8)2-Pts
O

(1-Octanol

H2N

HPLC, 99%, Sigma-Aldrich)

O
O

CH3
CH3

Asp-(C14)2-Pts

CH3

H2N

(1-Decanol, 99%, Sigma-Aldrich)

CH3

Table1. Unbranched structures

Similarly, the reaction involved with longer tail need longer time to collect water,
and the reaction time vary from 4 to 10 hours. However, these straight-chain tail
surfactants are insoluble in dodecane. Thus, we didnt devote mush attention to them.

2.1.4 Dow free amine Surfactant and Asp-(C8b)2-(SO4)

We have chance to obtain some pre-purified sample surfactant directly from Dow
Chemical Company, the tag shows its pure free amine (Asp-(C8b)2). However, the
CH3
CH3

O
H2N

different from what we have from above synthesis. Thus, we tried

O
O
O

surfactant is yellow and not very viscous liquid, which is very

to synthesis some surfactant replacing pTs with sulfuric acid, with

CH3

the same mole proportion and scheme. The products appearance is

CH3
DOW surfactant

similar to Dow sample, with yellow color and low viscosity. In this

reaction, the time is similar to synthesis of Asp-(C8b)2-(pTs), but one should be very
careful about the heating process. Since concentrated sulfuric acid replaced pTs in this
reaction, its easily to be charred the materials and fail, so the heating should be well
controlled.
Similar with Asp-(C8b)2-(pTs), we believe the purification process will remove the
ionic part from the head group, form a mixture of free amine and ionic surfactant.
The differences between Asp-(C8b)2-(pTs) and Asp-(C8b)2-(SO4), besides the
remaining, ionic attached molecule, the proportion of free amine and ionic part are
different too: the result shows Asp-(C8b)2-(SO4) behaves more like free amine, while
Asp-(C8b)2-(pTs) still have some ionic surfactant properties.

CH3

CH3

CH3

CH3

HSO4- H3N+

H2N
O

CH3

CH3
CH3

CH3

Figure 3. Asp-(C8b)2-(SO4 ) with counter ion and without counter ion( free amine)

2.2 Purification
First step to purification is carried out using Vacuum Pump Rotary
Evaporator(Rotavapor R-114, BUCHI) , for toluene, the water bath temperature
setting is about 60

. Second, to obtain the sample with higher purity, CombiFlash

Chromatography(CombiFlash Rf 200i, TELEDYME ISOS) is applied to the mixture

of production after vaporizing the solvent Toluene. After evaporation, synthesis
products are clear and highly viscous liquid. Applied CombiFlash, the product after
rotated vaporizer is taken and then being dissolved in solvent, which is also the
mobile phase of CombiFlash, conducted the next step purification. The process is
carried out with parameter as below:
Separation Column properties: RedisSep Column with 120g Silica
Sample load each time: 12g mixture
Flow Rate: 85 ml/min
Solvent: 95% Chloroform + 5% Methanol
Detector Wavelength: 254nm(Red) & 280nm(Purple)
Evaporative Light Scattering (ELS) : on
Spray Temperature: 30
Drift Temperature: 60
Other parameter is set as default.

3. Experimental Result
Related apparatus and chemicals suppliers show as below:
Purification Chromatography: CombiFlash Rf 200i, TELEDYME ISOS
10

Vacuum Rotavapor: Rotavapor R-114, BUCHI

Mass Spectrometry: LCQ ESI/APCI Ion Trap, Thermo-Fisher
Conductivity Meter: Non-aqueous Conductivity Probe DT700,
Dispersion Technology
Dynamic Light Scattering (DLS): Zeta Sizer Nano, Malvern
Dodecane (Solvent): n-Dodecane, for synthesis, EMD Millipore
3.1 Purification and Composition Analysis
To identify the product sample collected from purification, the Mass Spectrum is
applied to identify the molecular weight of the sample, making sure the sample
collected is objective product.
3.1.1 Purification: CombiFlash Solvent
CombiFlash mainly carries products purification. To choose a better solvent, two
different composition solvents are applied in the process:
i. 90% Ethyl acetate (HPLC, EMD Millipore) + 10% Chloroform (HPLC, EMD
Millipore)
ii. 95% Chloroform +5%Methanol (HPLC, EMD Millipore)

Figure4. CombiFlash Result with Solvent i.

11

Figure5. CombiFlash Result with solvent ii.

Figure 4 shows that separation result of Asp-(C8b)2-pTs with 90% Ethyl acetate +
10% Chloroform. At around 1 min, there is little red (UV, 254nm wavelength)
absorbance peak. From the CombiFlash operation manual, this peak should have a
benzene structure, which could be the remaining solvent toluene, since 254nm
wavelength is signature absorbance of a benzene ring. And at the time around 2min
and 3min, it shows two peaks on graph, but not completely separate, it might be a
mixture of product and unreacted pTs.
Figure 5 is the separation result with 95% Chloroform + 5% Methanol. Similar as
Figure 4, at around 1 min, there shows a absorbance peak in of 254nm wavelength,
however, different from figure1, there is only one peak at around 2min-3min,with a
high absorbance of evaporative light scattering detector (ELS, the green one,
evaporative light scattering) and comparatively lower absorbance of 254nm
wavelength, which is verified by mass spectroscopy to be objective product. The third
peak appears at a time of 9-10min, with absorbance of 254nm wavelength and ELS,
which is considered to be the un-reacted pTs.
Comparing the two different results coming from different solvents, the separation
is more complete with solvent ii, and it also give an obvious signal without overlap.
Thus, the conclusion could be made that solvent ii is more suitable for the separation.

12

3.1.2 Purification Peak Analysis and Mass Spectrometry Result

Peak identification
To make sure we are collecting the right product, identification the component of
every peak on Figure1 is very significant. Since the first peak on Figure 2 only has
254nm absorbent, it should be very similar to benzene. For our mixture, the only
possibility is un-dried toluene.
For the second peak, there is both peak of ELS and UV (254nm) with the strongest
signal, which indicate that it might be the remains out after the solvent has been
evaporated, and it might have one or more functional group with UV absorbance.
Thus, we assume the second peak is the desired product.
The third peak is much weaker compared with peak 2, and it also shows ELS
absorbance and UV absorbance. We assume that the peak2 is objective product and
peak3 is remaining pTs. Here is the rationale: 1. Judging from intensity that peak2s
signal is higher than peak3. 2. The retention time in silica gel column of each
component is related to their polarity, components with higher polarity tend to have a
longer retention time in column. Thus, the eluted order should be Toluene > desired
product (Asp-(C8b)2 in this case)> pTs.
The Mass Spectrum result* proves the assumption. The results showing a very high
peak with molecular weight of 358, which is exactly the molecular weight of Asp(C8b)2. And to identify the component of peak 3, pure pTs solution is prepared and
run by CombiFlash alone, the result is show on figure3. Compared with the peak3 on
figure2, the shape is very similar: A wide absorbance both in ELS and UV, the ELS
absorbance is higher then UV; the retention time of peak on figure 2 is 10min and on
Figure 6 is 5min, since the later one is on pure pTs, the retention time might be
shorter, it is reasonable to believe that peak 3 is pTs, Therefore, for rest purification,
the sample of peaks 2 are collected.

13

Figure 6. Pure pTs CombiFlash Result

Composition Analysis of Objective Product

Mass Spectrometry result of Asp-(C8b)2 shows under positive mode, which proves
that the objective product is obtained. From the negative mode result, we can see a
weak signal peak of 171, which is the molecular weight of pTs. This peak is also
show on other surfactants MS negative mode result with varied but weak intensity.
From the he negative mode result, we could assert that, there is no or not much pTs
or other counter ion attached at the head group because TLC (Thin-layer
chromatography) method might removed the pTs while separation. However, we still
can see a small peak on Mass Spectrometry graph, indicating there is still some pTs
attached on the molecule. Thus the product obtained after Combiflash might be a
mixture of Free Amine with no pTs attached and product with pTs, like what we
state before, which can also be supported by Figure 5.
On Figure 5, there is a UV absorbance peak for our product, indicating a functional
group like aromatic group or conjugated structure exists, however, our product
doesnt have these kinds of function group. Two possible reasons for this case:
1. The absorbance is cause by some Rayleigh Scattering. Its possible that some small
product particle in the solution that causes a Rayleigh scattering and gets
misunderstood by the detector as UV absorbance. It can be verified by doing a fulllength range of light absorption, if thats this case, the graph will be very different
14

from real UV absorbance.

2. Just like what we state before, the absorbance is caused by some remaining
attached pTs on molecule.
Thus, to try to get rid of remaining pTs and obtain pure free amine product, the
peak 2 sample coming from first CombiFlash run are collected and do the second run
with a new silica gel column.

Figure 7. Second run of purified sample

Only one peak shows on Figure 7, the plateau might be because loading sample
reaches to columns upper bound. The peak with strong signal should be the product,
however, the UV absorbance is still here, and at retention time of 6min, there is a very
weak ELS absorbance peak. The explanation is run CombiFlash multiple times might
be helpful to purified product, but it is not realistic. More studies need to be done to
obtain pure free amine product, like modify the solvent.
For other synthesized products, Asp-(C12b)2-(pTs), 470.3(product) on positive
mode, 171 on negative mode, but the intensity is lower than Asp-(C8b)2-(pTs),
indicating that pTs attached on Asp-(C12b)2-(pTs) might be easier to be removed by
CombiFlash; Dow Free Amine, 358(product) on positive mode with a high intense,
and nothing on negative mode; Asp-(C8b)2-(SO4), 358(product) on positive mode
with a high intense, and a very weak HSO4- peak(97) on negative mode.
The result indicate the main composition of product Asp-(C8b)2-(pTs) and Asp15

(C12b)2-(pTs) should be free amine, but still with some sample attached with pTs.
Particularly, the composition of attached pTs one should be fewer in C12 sample;
Dow surfactant should be high purity free amine; Most Asp-(C8b)2-(SO4) should be
amine with few Asp-(C8b)2 attached with HSO4-.
3.2 Solubility of Surfactant
Solubility of objective product is an important topic since the main goal is to study
the electrical property in nonpolar media (oil phase). In this case, dodecane is used as
nonpolar media because dodecane-AOT is well studied. After purify the product and
dried all solvent, the surfactants are in different physical form. And then we dissolve
them in dodecane (0.1gram sample in 10 gram solvent), however, the solubility in
dodecane of these surfactant are very different.
Solubility in

Surfactant Name

Physical form

Asp-(C6)2-(pTs)

white,fragile, crystalline

No

Asp-(C8b)2-(pTs)

clear,viscous,liquid,no color

Yes

Asp-(C8)2-(pTs)

white,fragile, crystalline

No

Asp-(C8b)2-(SO4)

clear,viscous,liquid, light yellow color

Yes

clear,viscous,liquid, light yellow color

Yes

Asp-(C12b)2-(pTs)

clear,viscous,liquid,no color

Yes

Asp-(C14)2-(pTs)

white,wax-like solid

No

Dow Sample
(Asp-(C8b)2)

dodecane

Table 2.

What obvious from the table is that surfactants solubility does not depend on
carbon chains length, but depend on branch on main chain. It could be found that all
soluble surfactants have branches in main carbon chain of the tails, while insoluble
one do not. The branches structure also affects their physical form, the straight chain
surfactants are all solid and branches surfactants are viscous liquid.
One interesting fact is that, from previous work done by Allison, surfactant Asp(C8b)2-pTs (with pTs attached) is insoluble in dodecane. In her work, the purification
16

was carried out by GPC (Gel permeation chromatography) which will not split pTs
from surfactant, and the MS result proved that pTs is attached on head group.
Therefore, an assumption can be draw that pure pTs surfactant is insoluble in
dodecane, while free amine surfactant is soluble. The solubility of free amine
could reach 10%( mass concentration) or even higher.
3.3 Conductivity and Micellar Aggregation
Conductivity and micellar size are two important properties of micelle solution, we
try to find our some kind of relationship between conductivity and micelle size, and
then compare with the commercial surfactant AOT. In this part, the source of AOTs
conductivity data is from published work by Dufresne[20].
3.3.1 Conductivity
The overall conductivity vs. concentration result shows as Figure 5, which shows
the tendency that how conductivity change with a concentration regime from 0.1% to
10%. Since only Asp-(C8b)2-(pTs), Asp-(C12b)2-(pTs), Asp-(C8b)2-(SO4), and Dow
Sample are soluble in dodecane, we only discuss these 4 surfactants solution. From
the figure, since the conductivity of pure dodecane is in a order of magnitudes of E-11,
its obvious that all surfactants help increase dodecanes conductivity, and the general
trend is as surfactants concentration increasing, solutions conductivity also
increasing. The solutions conductivity is proportional to surfactants concentration in
both two regimes (low concentration and high concentration), with different slope.
Particularly, Asp-(C8b)2-(pTs) conductivity is much higher than any other surfactants
solution. And the overall conductance order is:
Asp-(C8b)2-(pTs)> AOT>Asp-(C12b)2-(pTs)>Asp-(C8b)2-(SO4).

17

Figure 8. Overall Conductivity Tendency

To show the exponent correlation of these surfactant in dodecane, we plot the

conductivity vs. Mass concentration in log-log graph for surfactants AOT, Asp(C8b)2-(pTs), Asp-(C8b)2-(SO4) and Asp-(C12b)2-(pTs). Do power fitting at range
of 1%-10%, we obtain the exponent of the data.
Surfactant Solution

Exponent

Asp-(C8b)2-(pTs) in dodecane

2.18

Asp-(C8b)2-(SO4) in dodecane

1.26

Asp-(C12b)2-(pTs) in dodecane

1.17

AOT in dodecane

1.26

AOT in Heptane

0.52

Asp-(C8b)2-pTs in Toluene

1.17

Table 3.

18

Conductivity vs. Concentration

Conductivity vs Mass Concentration

1000

1000
Asp-C12b-pTs
Asp-C8b-pTs
Asp-C8b-SO4
AOT

Asp-C12b-pTs
Asp-C8b-pTs
Asp-C8b-SO4
AOT
100
Conductivity (nS/m)

Conductivity (nS/m)

100

10

10
1

0.1
0.1

1
Mass Concentration%

10

1
1

10
Mass Concentration%

Figure 10. Power fitting of log-log

Figure 9. Log-log Conductivity

conductivity

From Figure 10, we can see, most surfactant solutions behavior is consistent with
power fitting in log-log graph. For AOT, Asp-(C8b)2-(SO4) and Asp-(C12b)2-(pTs),
the exponent( slope) are around 1.2, however, for Asp-(C8b)2-(pTs) shows an
exponent of 2.18. It means from mass concentration 1%-10%, the correlation could
also be described as second power exponent function (and linear-linear mentioned as
above), which is abnormal than other surfactants solution. We think its related to the
micelle formation.

Dow free Amine, Asp-(C8b)2-(SO4) and Asp-(C8b)2-(pTs)

Figure 11 compares conductivity of Asp-(C8b)2-(SO4) &Dow sample in a low
mass concentration range( 0.1% to 1%); Figure 12 shows the conductivity of Asp(C8b)2-(SO4) and Asp-(C8b)2-(pTs) in a concentration range of 0.1% to 10%. From
Figure 11, we can see that at low concentration, the conductivity behavior of Dow
free amine is very similar to the Asp-(C8b)2-(SO4), while Figure 12 shows, pTs
ones conductivity is higher than SO4 ones by about 20 times. This result indicates
19

that this three surfactants, even though them have the same main chemical component,
Asp-(C8b)2 free amine, there must be something different among their components,
and that should be the reason why their conductivity behaviors are so different (It
would be good that we have Dow samples conductivity result in a same
concentration range, but we dont have enough Dow sample to conduct this
measurement).

Figure 11.Conductivity of

Figure 12.Conductivity of Asp-(C8b)2-

Asp-(C8b)2-(SO4) &Dow sample

(SO4) &Asp-(C8b)2-(pTs)

From Figure 11, since the conductivity result in low concentration are very similar,
combine with MS result, it might be reasonable to conclude that the components of
Dow sample and Asp-(C8b)2-(SO4) are similar. However from figure 12, the
difference between Asp-(C8b)2-(SO4) and Asp-(C8b)2-(pTs) is very huge. We can
see that, for both linear regime, low concentration and high, Asp-(C8b)2-(pTs)s
conductivity is 20 times higher than Asp-(C8b)2-(SO4) .
One possible explanation is that, if Dow sample is real free amine, then Asp(C8b)2-(SO4) is more like to be free amine mix a small part of SO4 attached.
However, Asp-(C8b)2-(pTs) might still have some part of molecule attached with pTs
at their head group. Which means, its a mixture of free amine and cationic surfactant
as we mentioned in previous chapter. And that might be the reason why the
conductivity behavior is such a difference.
20

Another information shows on Figure 12, for both surfactants, there is a turning
point in a certain mass concentration: both of them are around 6% or 5%. And both
range divided by this point shows a good linear fitting. For Asp-(C8b)2-(SO4), high
concentration slope is 3 times higher than low concentration regime; For Asp-(C8b)2(pTs), the multiple is over 10 times. This might related to the CMC: its possible that,
before this point, it is the dimer or other pre-micelle aggregation unit helps increase
the conductivity, and the point should be the critical micelle concentration (CMC) of
the surfactant. However, previous work shows the CMC (critical micelle
concentration) of AOT in dodecane is about 1mM in dodecane (about only 0.6% in
mass concentration), with an aggregation number of 30 [21]. Therefore, this problem
should be discuss later, in the summary part, after we show the conductivity graph of
AOT compared with Asp-(C8b)2-(pTs).

AOT and Asp-(C8b)2-(pTs)

Figure 13 and figure 14 shows the regular and log-log Conductivity vs. Mass
Concentration for surfactants solution Asp-(C8b)2-(pTs) and AOT in a mass
concentration range of 0.1% to 10%. Same as first part, Asp-(C8b)2-(pTs) has a much
higher conductivity than AOT, almost about 10 times. And theres also a turning point
for both surfactant solution, in both high concentration and low concentration regime;
The correlation of both regime are linear, with a very good fitting. For AOT, the high
concentration slope is also 3 times higher than lower regime, which is the same with
Asp-(C8b)2-(SO4) and Dow free amine.
One interesting thing is, if we assume Asp-(C8b)2-(pTs) is a mixture of cation
surfactant and nonionic surfactant, and that is the reason why it cause such a higher
concentration than Asp-(C8b)2-(SO4) and Dow sample. Then, AOT is anionic
surfactant, however its conductivity enhancing ability is lower then mixture Asp(C8b)2-(pTs). One possible explanation is the electropolarity due to this difference,
which still need to be discussed.

21

Figure 13. Conductivity of Asp-(C8b)2-

Figure 14. Log-log Conductivity of Asp-

(pTs) and AOT

(C8b)2-(pTs) and AOT

Figure 15. Conductivity of

Figure 16. Log-log Conductivity of

Asp-(C8b)2-(SO ) and AOT

4
Asp-(C12b)2-(pTs) and Asp-(C8b)2-(pTs)

Asp-(C8b)2-(SO4) and AOT

AOT and Asp-(C8b)2-(SO4)

Figure 15 shows the conductivity comparison of AOT and Asp-(C8b)2-(SO4),
which means it might be the comparison of anionic surfactant with non-ionic
surfactant. It might look similar from the overall figure (figure 8), but in the separated
22

plot we can find that the conductivity of AOT is 2 times higher than A-(C8b)2-SO4.
Besides, the turning point and the linear proportional correlation between mass
concentration and conductivity, are just like Asp-(C8b)2-(pTs).
Figure 17 is the conductance comparison between Asp-(C8b)2-(pTs) and Asp(C12b)2-(pTs). From part 2 we can see, these two products share the same synthesis
and purify process. Since it shows that Asp-(C8b)2-(pTs) might be the mixture of
cationic surfactant and nonionic surfactant, it make sense to say Asp-(C12b)2-(pTs) is
also a mixture. However, the graph shows a different result: the conductivity is very
different between them, still, Asp-(C8b)2-(pTs) is about 10 times higher than Asp(C12b)2-(pTs). For the structure, the only difference is that the Asp-(C12b)2-(pTs)
has a longer tail than Asp-(C8b)2-(pTs). It might be possible that the longer tail is the
reason why its conductivity is much lower. But if we compare its linear slope to
Asp-(C8b)-(SO4), we can find that the behavior is very similar, so, it might be
component is the reason cause the difference. Asp-(C12b)2-(pTs) has less ionic part
than Asp-(C8b)2-(pTs), more like free amine, and pTs is more likely be removed
from the surfactant which has a longer tail like Asp-(C8b)2-(pTs).

Figure 17. Conductivity of Asp-(C8b)2-

Figure 18. Log-log Conductivity of Asp-

(pTs) and Asp-(C12b)2-(pTs)

(C8b)2-(pTs) and Asp-(C12b)2-(pTs)

23

3.3.2 Micellar Aggregation Analysis

In this part, the DLS size measurement on surfactant solution of Asp-(C8b)2-(pTs)
and Asp-(C12b)2-(pTs) which is conducted by Xiaoyu Liang, is showed as below.
The AOTs micelle size data is from Bens work.
Micelle Size diameter (nm)
mass concentration

Asp-(C8b)2-(pTs) Asp-(C12b)2-(pTs)

AOT

5%

2.578

2.331

NA

10%

3.587

2.845

3.3

Table 4.

From the result, we can see, at 10% concentration the micelle size:
Asp-(C8b)2-(pTs)> AOT> Asp-(C12b)2-(pTs)
This result is consistent with the conductance order we have above. It might indicate
fours points for reverse micelle in dodecane:
1. Larger micelle size induces higher conductivity.
2. Longer tails induce a larger micelle size.
3. For the same structure, non ionic and cationic mixture surfactant might form a
lager micelle at a same concentration.
4. Concentration could be a factor that affects the micelle size.
We do full range of concentration for Asp-(C8b)2-(pTs) and Asp-(C12b)-(pTs), but
the Zeta Sizer shows a very poor correlation function for those concentration lower
than 5%. Only above 5%, the correlation function shows reasonable, and for 10%, the
correlation function is very smooth. One possible reason is, under 5%, the molecule
aggregation size is too small to be detected. It might be that whats forming at the low
concentration is mixture of reverse micelle and pre-micelle structure. One abnormal
thing is, in aqueous solution, the aggregation number is independent on concentration,
but our result shows, at different concentrations, the micellar sizes are different. Think
about Mullers works[14], AOT is the type II ionic surfactant, which form reverse
micelle structure in nonpolar media, but there still some evidence shows it has some
type Is characters( forming oligomers). This suggest that there is no pure type I or
pure type II. And it might be a possible explanation to what we observed.
24

4. Discussion
From the result above, we can see Asp-(C8b)2-(pTs) is a mixture of pure free
amine and pTs attached surfactant, which means they a mixture of ionic
surfactant and non-ionic surfactant; Dow sample and Asp-(C8b)2-(SO4) might be
more like non-ionic surfactant, and Asp-(C12b)2-(pTs) is the also the mixture, but
different from Asp-(C8b)2-(pTs), we believe most of the component should be free
amine. This conclusion is supported by MS and Combiflash result, and also can be
verified by conductivity measuring. This result indicates that, the pTs ion is easier
separated if the head-group is attached with longer tail like C12b, because its more
non-polar.
When added to dodecane, this surfactant solution shows different properties. We
find out only the structure with branches that are soluble in dodecane. And the
surfactant solution shows a different conductivity behavior along concentration:
A-(C8b)2-(pTs)> AOT>A-(C12b)2-(pTs)>Asp-(C8b)2-(SO4)
This order is consistent with micellar size data, however, because the proportion of
ionic part and non-ionic part is hard to estimate, we know simply imply that is the
molecule structure that cause the differences.
By now, we can make an assumption that, DOW sample, Asp-(C8b)2-(SO4) and
Asp-(C12b)2-(pTs) should be more like non-ionic surfactant, maybe with some
cationic impurities; AOT is anionic surfactant; Asp-(C8b)2-(pTs) is a mixture of
cationic surfactant and nonionic surfactant. By seeing Figure 12, 13 and 17, we can
find that cation surfactants conductivity (Asp-(C8b)2-(pTs)) is much higher than
non-ionic surfactant solution and anion surfactant solution, by about 10 times for Asp(C8b)2-(SO4) and 5 times for AOT, while AOT solutions conductivity is 2 times
higher Asp-(C8b)2-(SO4). Thus, this result indicate that: for a surfactant with same
structure (head group and tails) the conductivity enhance ability should be: cation
surfactant> anion surfactant> non-ionic surfactant.
If we plot the conductivity data in regularly with linear axis, the correlation between
concentration and conductivity are linear in both low regime concentration and high
25

regime, and the high regimes slope is greater than low regime. The linear proportion
is consistent with strong electrolyte aqueous solution. However, when about 5%6%( 80mM-90mM) there is a turning point shows( thats how we divide high and low
concentration regime). For Behrenss work of the non-ionic surfactant span 85 in
hexane, there is a turning at around 25mM, above the CMC for 10mM[22]. For DLS
data of Asp-(C12b)2-(pTs) and Asp-(C8b)2-(pTs), we can see the micelle structure
signal around 8mM and 10mM. Thus, the turning points are actually above CMC,
rather than CMC. For CMC, not dramatic turning is observed, which might be
explained by Morrisons work[3].
Even though the slope change is not very dramatic, but its worth to pay attention
because the DLS also shows, when below that point, the micellar size is fluctuating
and the correlation function is very poor. Therefore, one possible reason is that there
should be some micelle structure change occurs at this point. Maybe the molecular
start form a more stable aggregation cluster with larger aggregation number.
Furthermore, if we plot it on log-log plot, we can find that by doing power fitting,
the exponent for Asp-(C8b)2-(pTs) reaches to 2.2, while others just around 1.2. Most
previous work shows, if the surfactant form a micelle structure in non-polar media,
the conductivity should be linear proportional to concentration[22, 9] (above CMC), or
conductivity ~c0.5 (concentration)[9](below CMC).
In Dufresnes work[9], a system of AOT in hexane is study, the below CMC part is
explained by weak dissociation that the law of mass action required
[Na+]=[AOT-] ~ [NaAOT]1/2. And for the above CMC part, one common explanation
is applied to explain[9, 23]: the charged micelle is the charge disproportion theory that
two originally neutral micelles exchange charge, forming two micelles with opposite
charge. In Behrens work[22], if the assumption of a monovalent micelle is made, a
expression of conductivity and concentration is generated:

= e 2 (C+1 + C1 ) / = e 2C0 /

= 2 exp( B / 2a)
Where C0 is the concentration of AOT and
26

is equilibrium fraction of the charged

micelles, B is the solvents Bjerrum length, which is independent with micelle, and
2a is the Born diameter, which is identified with the size of the hydrophilic micelle
head group core where charge reside ;

is the friction coefficient involved with the

micelles hydrodynamic radius which can describe by Stoke equation: = 6RH ,

where RH is the hydrodynamic radius of micelle and is viscosity of solution.
Obviously, above equation explained why the conductivity above CMC should have
linear correlation with concentration. However, for Asp-(C8b)2-(pTs) is consistence
with this equation. One possible reason might be the surfactant Asp-(C8b)2-(pTs)
form a mix micelle with both free amine molecule and pTs molecule. Recall the
previous work[15], the pure Asp-(C8b)2-pTs (cationic surfactant) is insoluble in
dodecane, even soluble in toluene, when doing the DLS size measuring, there is no
signal showing micelle formation (which is explained by Mullers theory[14] that the
pure pTs surfactant form some oligomers rather than micelle because of
comparatively large head-group radii). This fact is reasonable, since dodecane is more
non-polar than toluene, so the surfactant with a more polar ionic head group is
insoluble. However, Asp-(C8b)2-(pTs) can be dissolved in dodecane.
Thus, it indicates that, maybe that is the free amine (non-ionic surfactant) cause
the solubility in dodecane, which is more non-polar than toluene. And, in contrast, the
cationic component causes a higher conductivity. The possible reason might also be
this mixture surfactant form a mix reverse micelle. Previous works prove its possible
to from a mixed micelle both in aqueous media and non-polar media, but no enough
research report that how this structure, especially the ionic head group will affect the
micelle solutions electrical property.

Figure 18. Possible mixed reverse micelle structure of Asp-(C8b)2-(pTs)

27

5. Conclusion
Some AOT structure surfactants were synthesized: Asp-(C8b)2-(pTs), Asp(C12b)2-(pTs) and Asp-(C8b)2-(SO4), plus a surfactant sample from Dow(Asp(C8b)2). Combiflash instrument is applied to purify the surfactant, and mass
spectrometry, Solubility, Conductivity and DLS is applied to analyze the surfactant
solution in dodecane. The solubility result shows that, only branched-tail surfactants
are soluble in dodecane. And combine the result from MS and conductivity, we can
say the Combiflash will wipe off the ionic part from surfactant in different extent,
cause the product into free amine or free amine mix with ionic surfactant.
And all of these surfactants can enhance the dodecanes conductivity in different
level, which might be effect by the surfactants structure and component. For all
surfactant, there are turning point shows on regular conductivity vs. concentration plot,
the correlation is linear for both high concentration and low concentration, and the
slope in higher concentration regime is greater than lower concentration regime.
Combine with DLS measurement, we can see the micellar size is varied with
concentration, which it different with AOT, which might due to some oligomers
formed in this system. Besides, Among these surfactant, Asp-(C8b)2-(pTs) can
improve dodecanes conductivity much more efficiently by other surfactants.
By plotting the conductivity data in log-log graph, its obvious that Asp-(C8b)2(pTs) behave differently than other surfactant, showing a exponent of 2.2 while others
are about 1.2. To explain this abnormal behavior, and a possible explanation of mixed
reverse micelle is rising. The result shows its possible that conductivity and
concentration not obey a linear correlation even above CMC.
Even though we do have some progress, there still are some futures works need to be
done. Such as modifying the purification to obtain the pure ionic surfactant and nonionic surfactant then measuring the micelle size and conductivity, it would be helpful
to verify whether the mixture could actually enhance the solubility and conductivity.
28

Since most the AOTs conductance is greatly affected by water, we should also
devote attention to the waters concentration in the solution.

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