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Surface Behavior of Aqueous Solutions of Sodium Lauryl Ether Sulfate,

Additives and Their Mixtures: Experimental and Modeling Study

Article in International Journal of Thermophysics · October 2020

DOI: 10.1007/s10765-020-02738-0

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International Journal of Thermophysics (2020) 41:166
https://doi.org/10.1007/s10765-020-02738-0

Surface Behavior of Aqueous Solutions of Sodium Lauryl

Ether Sulfate, Additives and Their Mixtures: Experimental
and Modeling Study

Shahin Khosharay1 · Mahsa Rahmanzadeh2 · Bahman ZareNezhad2

Received: 19 July 2020 / Accepted: 10 September 2020

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
The surface tensions of aqueous solutions of sodium lauryl ether sulfate (SLES),
ethanol, acetonitrile, 1-propanol and 2-propanol were individually measured using
the pendant drop technique. Then, the surface tensions and critical micelle concen-
trations of the mixed aqueous solutions of (SLES + additives) were then measured
at different concentrations of species for the first time. All measurements were con-
ducted at the temperature of 298.15 K. In addition, a thermodynamic model was
presented for accurately predicting of the surface tensions of the mixtures and the
surface coverage of the surfactant in the mixture with the average absolute deviation
of 1.45 %. Furthermore, an increase in the SLES concentration led to a higher sur-
face coverage, although the presence of an additive caused a slight decrease in the
surface coverage of SLES and an increase in the critical micelle concentration of the
mixtures.

Keywords Additives · Critical micelle concentration · Sodium lauryl ether sulfate ·

Surface tension · Thermodynamic model

List of Symbols
a Interaction parameter
AAD Average absolute deviation
b Surface-to-solution distribution constant
c Concentration
de Maximum diameter of the droplet
ds Small droplet diameter
g Gravitational constant
H Shape factor of a droplet

* Shahin Khosharay
[email protected]
1
Iranian Institute of Research & Development in Chemical Industries, Tehran, Iran
2
School of Chemical, Petroleum and Gas Engineering, Semnan University, Semnan, Iran

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166 Page 2 of 17 International Journal of Thermophysics (2020) 41:166

R Ideal gas constant

T Temperature
V Molar volume
x Mole fraction

Greek Letters
α Bulk phase
γ Activity coefficient
Γ Surface excess
θ Surface coverage
𝜇i Chemical potential of component i
π Surface pressure
ρ Density
σ Surface tension
Δ Difference
ω Molar area

Subscripts
b Bulk
c Critical
calc Calculation
exp Experimental
i Component i
S Surface
0 Water
1 Surfactant or additive

1 Introduction

Mixed surfactant systems have been experienced in different applications since they
perform better than single surfactants. In addition, the application of mixed systems
improves some physicochemical properties such as ionic strength, pH, and viscos-
ity. Mixed surfactant systems are significant in several areas, including detergency,
emulsification, medicine and enhanced oil recovery. Furthermore, a mixture of sur-
factants has frequently better surface properties compared to individual surfactants,
and they can demonstrate synergism. For example, the mixture of the (ionic + non-
ionic) surfactants exhibits strong synergism. Additionally, the synergistic behavior
of mixed surfactant solutions helps reduce the total amount of surfactant, thus they
result in reducing the cost and environmental disadvantages. Previous researches
have extensively evaluated the effect of additives on micellization behavior because
they have potentials in many scientific and industrial aspects. For instance, alcohols
can strongly affect the physicochemical properties of a micellar solution. Therefore,
the physicochemical properties of such mixed solutions have attracted much atten-
tion in the realm of amphiphiles [1–4]. The reduction of the critical micelle concen-
tration (CMC) of ionics in the presence of the salt is well-known and attributed to

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International Journal of Thermophysics (2020) 41:166 Page 3 of 17 166

the screening effect of that salt on electrostatic repulsions between surfactant head-
groups in the micelles. However, the CMC may reduce less in the case of nonionics
since only the weak salting-out effect of the salt is prevalent [5, 6, 8].
In addition, additives affect the micellization behavior of surfactants through non-
chemical interactions [7]. More precisely, the deviation from the ideal state is used
to determine the properties of (surfactant + additive) aqueous solutions. This non-
ideality can be described by using an interaction parameter [8]. Therefore, knowing
about how these additives interact with surfactants is important [3]. The interaction
parameter can be regressed through some models and based on experimental sur-
face tensions. Such interaction parameters are applied for describing the adsorption
behavior of (surfactant + additive) systems. The other group of models requires the
features of individual surfactants and additives in addition to the interaction param-
eter. For example, the surface equations of state need the isotherm parameters of
pure surfactants and additives [9]. Among various mixed systems, the mixtures of
an anionic surfactant and an additive have attracted much attention due to their wide
application, especially in the realm of detergency [2]. Furthermore, the mixtures are
important from the fundamental and industrial viewpoints since they have strong
synergism due to complimentary behavior of the mixed micelles [10].
Alkyl ether sulfates (AESs) are considered as an important group of anionic
surfactants. The basic structure of such surfactants is R–(OCH2CH2)x ­OSO3−M+,
where x represents the number of oxyethylene (OE) groups in the alkyl chain. The
OE units can increase the solubility of these surfactants in water. Additionally, these
surfactants have the potential for combining the advantages of both anionic and non-
ionic surfactant types. In addition, AESs are extensively applied in shampoo formu-
lations, skin cleansers, creams, and household detergents [11, 12]. Based on their
wide range of applications, evaluating the physicochemical properties of AESs in the
aqueous solutions of additives is necessary [4]. Sodium lauryl ether sulfate (SLES)
is one of the significant anionic surfactants of this group, and C ­ 12H25 ­(OCH2CH2)x
­OSO3Na is its basic structure. It has one to four hydrophilic OE groups, which are
adjacent to the anionic sulfate group. On the other hand, no physicochemical prop-
erties of the aqueous solutions of (SLES + alcohol) have been reported in literature
[13].
The present study focused on the aqueous solutions of SLES in the presence of
additives, including ethanol, 1-propanol, 2-propanol, and acetonitrile. First, the sur-
face tension of the applied aqueous solutions of individual substances was measured
by using the pendant drop technique. Then, a thermodynamic model based on the
equality of chemical potentials was applied to the surface tensions of aqueous solu-
tions. These measurements were for the aqueous mixtures of (SLES + additives).
Furthermore, the experimental surface tensions were used to measure the CMCs. By
using the presented thermodynamic model, the surface coverage was computed for
the aqueous solutions of (SLES + additives), followed by discussing the effect of the
employed additives on the interfacial behavior of SLES.

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166 Page 4 of 17 International Journal of Thermophysics (2020) 41:166

2 Experimental

2.1 Materials

SLES with high purity was purchased from Kimiagaran Emrooz, Iran. Ethanol,
1-propanol, 2-propanol, and acetonitrile were provided from Merck, Germany.
Additionally, distilled water was employed in each experiment in order to prepare
the solutions. Next, a digital electronic balance with uncertainty of ± 0.1 mg was
used to weight the materials. Finally, the densities of aqueous solutions were meas-
ured with a glass pycnometer. The specifications of the employed materials are pre-
sented in Table 1.

2.2 Apparatus

A pendant drop apparatus was applied to measuring the surface tensions of aque-
ous solutions. Figure 1 displays the schematic of the applied pendant drop appara-
tus. All experiments were conducted in a cylindrical glass cell with a total volume
of 500 cc. Two sight glasses of the cell allow a user to observe the droplet from
a horizontal axis. In addition, this set-up has a glass capillary tube for creating a
hanging drop. The inner and outer diameters of the applied capillary tube were 1.2
and 1.6 mm, respectively. The sample of each aqueous solution was injected into
the cell with a needle valve, and a pendant drop was formed at the tip of the capil-
lary tube. This system can operate at the ambient pressure and temperature range
of (275.15–373.15) K. Also, a PT100 thermometer (Pro-Temp Controls, Santa Ana,
California, United States) with an accuracy of ± 0.1 K was used for measuring the
temperature, followed by employing a high-resolution digital camera in order to cap-
ture the images of the drops and measure the surface tension of each aqueous solu-
tion. The uncertainty of the surface tension measurements was about ± 0.3 mN·m−1.

2.3 Experimental Procedure

Prior to any measurement, the overall apparatus was washed with distilled water
three times as follows. Firstly, the inlet of the air was closed. The needle valve was
opened, and the vacuum pump was turned on. The deionized water was introduced
into the system from the top of the needle valve. The vacuum created by the vac-
uum pump led to the flow of deionized water in the needle valve and glass capil-
lary tube. Then, the compressed air was used to dry the cell and its connections. A

Table 1  The specifications of Chemical Purity Supplier

the applied materials used in the
experiments Ethanol 0.99 Merck, Germany
Acetonitrile 0.99 Merck, Germany
1-Propanol 0.99 Merck, Germany
2-Propanol 0.99 Merck, Germany

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International Journal of Thermophysics (2020) 41:166 Page 5 of 17 166

Fig. 1  The schematic diagram

of the apparatus for measuring
the surface tension of surfactant
solutions by the pendant drop
technique, 1 Needle valve; 2
Glass capillary tube; 3 Inlet
of the jacket; 4 Outlet of the
jacket; 5 Inlet of the air; 6 To
the vacuum; 7 Thermometer; 8
Digital Camera; 9 Light source;
10 Sight glass; 11 Jacket of the
cell; 12 Cell

solution with a certain concentration was made and injected into the pendant drop
cell by using a needle valve and capillary tube. Furthermore, a vertical pendant drop
was formed with a capillary tube, and the images of the drop were taken during the
experiment by a digital camera, followed by measuring the droplet dimensions. The
surface tension was calculated by using Eq. 1 as follows [14]:

Δ𝜌d2e g
𝜎= (1)
H
where ∆ρ and g indicate the difference of the density between gas and liquid phases
and the gravitational constant, respectively. Additionally, ­de is the maximum diame-
ter of the liquid droplet (in m) and d­ s belongs to the diameter of the liquid droplet
measured at a distance of ­de from the bottom of the droplet.( Eventually,
( )) the parame-
ter H was computed from [15] in terms of the shape factor H = f ds .
1 1 d
e

3 Model Description

This study uses a two-dimensional solution model for modeling the surface phase.
In two-dimensional solution model, the surface phase is considered as a mixture
which has the same components as the solution from which the adsorption is con-
ducted. The difference between the composition of surface phase (S) and the bulk
solution (α) is due to the surface force field, and it depends on the surface tension

13
166 Page 6 of 17 International Journal of Thermophysics (2020) 41:166

(σ). The other assumption of the model is that the monolayer exerts a film pressure
(π = σ0 − σ), known as a surface pressure. The molecules of solute absorbed at the
surface phase can move freely in the surface plane, but they cannot pass the barrier
(plane of surface). On the other hand, the molecules of the absorbed film have two-
dimensional translational energy, so the surface pressure is due to the bombardment
of the barrier with the absorbed molecules of the solute.
The surface tension model can be derived when chemical potentials in the liquid
phase and interface are set equal. The chemical potential of a component in the liq-
uid phase is calculated through Eq. 2:
( )
𝜇i𝛼 = 𝜇i0𝛼 + RT ln 𝛾i𝛼 x𝛼i (2)

where 𝜇i, 𝜇i0, and γ denote the chemical potential of component i, the standard
chemical potential, and the activity coefficient, respectively. In addition, x­ i, R, and T
represent the mole fraction of component i in the liquid phase, the universal gas con-
stant (8.314 J ­mol−1·K−1), and the absolute temperature, respectively. Furthermore,
the superscript α belongs to the liquid phase. The interfacial chemical potential is
expressed as follows:
The surface chemical potential is stated as follows:
( )
𝜇iS = 𝜇i0S + RT ln fSi xSi − 𝜎𝜔i (3)

where 𝜎 and 𝜔 denote the surface tension of the aqueous solution and the partial
molar surface area, respectively, and the superscript S belongs to the surface layer.
According to the thermodynamic equilibrium, the chemical potentials of compo-
nent i in the bulk and the surface layer are the same. Therefore, Eq. 4 can be written
in this regard:

𝜇i𝛼 = 𝜇iS (4)

A solvent (i = 0) at the standard state is considered as a pure solvent. This assump-

tion leads to xS0 = x𝛼0 = 1, fS0 = f𝛼0 = 1, and 𝜎 = 𝜎0
Equation 5 can be derived using the above-mentioned considerations and the
combination of the Eqs. 2–4.

𝜇00S − 𝜎0 𝜔0 = 𝜇00𝛼 (5)

( 𝛼 )
Furthermore, the assumption of the infinite dilute solution xi → 0 was used
for the standard state of the solute (i = 1) thus 𝛾1𝜎 = 𝛾1S and 𝜎 = 𝜎0. Using Eqs. 2–5,
Eqs. 6 and 7 are derived as follows [16, 17]:
( ) ( )
RT ln fS0 xS0 = − 𝜎0 − 𝜎 𝜔0 (6)

fS1 xS1 ∕fS10 1 ( )

ln =− 𝜎 0 − 𝜎 𝜔1 (7)
K1 f𝛼1 x𝛼1 RT

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International Journal of Thermophysics (2020) 41:166 Page 7 of 17 166

( )
where K1 = x𝜎1 ∕x𝛼1 x𝛼 →0 represents the distribution coefficient at the infinite dilu-
1
tion of the solute. Additionally, 𝜋 = 𝜎0 − 𝜎 and γ10 indicate the surface pressure and
infinite dilution, respectively. Equations 8 and 9 can be obtained from Eqs. 6 and 7.
RT ( S )
𝜋=− lnx0 + lnfS0 (8)
𝜔0

fS1 xS1 ∕fS10 𝜔1 ( S )

ln = lnx0 + lnfS0 (9)
K1 f𝛼1 x𝛼1 𝜔0

The relationship between surface mole fraction and surface coverage can be writ-
ten as follows:
𝜃k 𝜔i
xSk = ∑ � � , ni = , 𝜃 = 𝛤k 𝜔k (10)
nk i≥0 𝜃i ∕ni
𝜔0 k

where θ and 𝛤 denote the surface coverage and surface excess concentration, respec-
tively. In addition, 𝜔i and 𝜔0 belong to the molar surface area of the surfactant
and the solvent, respectively. For the aqueous solution of an individual surfactant,
Eqs. 11, 12, and 13 can be applied regarding the activity coefficients.
( ( ) ) ( )
1 1
ln𝛾0S = ln 1 − 1 − 𝜃1 + 1 − 𝜃 + a𝜃12 (11)
n1 n1 1

( ( ) ) ( )( )
ln𝛾1S = ln n1 + 1 − n1 𝜃1 + 1 − n1 1 − 𝜃1 + an1 𝜃02 (12)

( )
(13)
S
ln𝛾10 = lnn1 + 1 − n1 + an1

where a indicates the interaction parameter. Equations 11–13 are replaced into
Eqs. 8 and 9 with 𝛾1𝛼 = 1. Moreover, when Eq. 10 is used, Eqs. 6 and 7 can be
expressed in terms of the surface area fractions (coverages) instead of mole fractions
resulting in the realistic molecular geometry.
Therefore, the equation of state and adsorption isotherm is derived as follows:
( ( ) )
RT ( ) 1
𝜋=− ln 1 − 𝜃1 + 1 − 𝜃1 + a𝜃12 (14)
𝜔0 n1

𝜃1 ( )
bc = ( )n1 exp −2an1 𝜃1 (15)
n1 1 − 𝜃1

In Eqs. 14 and 15, c, b, and 𝜔0 are

( the concentration
) in the liquid phase, surface-
to-solution distribution coefficient bc = K1 x𝛼1 , and the molar surface area of the
water, respectively. In the present study, Eq. 16 was employed to the surface molar
area [18–20].

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166 Page 8 of 17 International Journal of Thermophysics (2020) 41:166

( ) 4∕15
𝜔0 = 1.021 × 108 V6∕15
c
Vb (16)

where ­Vb and V­ c (in c­ m3·mol−1) represent the molar volume and the critical molar
volume of the pure water, respectively, and 𝜔0 is in ­cm2·mol−1. In Eqs. 14 and 15, R,
T, 𝜔0, and c are the known parameters. Furthermore, a, b, and 𝜔1 indicate adjustable
parameters which can be determined by minimizing the mean absolute deviations of
the surface tension. The average absolute deviation of the surface tension is obtained
by Eq. 17.
N exp.
calc.
1 ∑ || 𝜎i − 𝜎i ||
AAD𝜎 = | exp. | × 100 (17)
N i=1 || 𝜎i |
|
where N is the number of experimental data, and π and θ demonstrate the unknown
parameters of the model calculated by the simultaneous solution of Eqs. 14 and 15.
Finally, the presented model regarding the aqueous solutions of (additive + sur-
factant) in the present study is expressed as follows:
( ( ) ( ) )
RT ( ) 1 1 2 2
𝜋=− ln 1 − 𝜃1 − 𝜃2 + 𝜃 1 − + 𝜃2 1 − + a1 𝜃1 + a2 𝜃2 + 2a12 𝜃1 𝜃2
𝜔0 n1 n2
(18)
𝜃1 ( ) (( )( 2 2
))
b1 c 1 = ( )n1 exp −2a1 𝜃1 − 2a12 𝜃2 exp 1 − n1 a1 𝜃1 + a2 𝜃2 + 2a12 𝜃1 𝜃2
1 − 𝜃1 − 𝜃2
(19)
𝜃2 ( ) (( )( 2 2
))
b2 c 2 = ( )n2 exp −2a2 𝜃2 − 2a12 𝜃1 exp 1 − n2 a1 𝜃1 + a2 𝜃2 + 2a12 𝜃1 𝜃2
1 − 𝜃1 − 𝜃2
(20)
where the value of ­a12 can be determined Eq. 21.
a1 + a2
a12 = . (21)
2
where θ1, θ2 and π are unknown parameters, which are calculated through the simul-
taneous solution of Eqs. 18–20.

4 Result and Discussion

The surface tension measurements of the aqueous solution of sodium lauryl ether
sulfate (SLES), ethanol, acetonitrile, 1-propanol, and 2-propanol were performed
at different species concentrations. Each experiment was conducted three times in
order to ensure that all measurements are consistent. Therefore, each experimental

13
International Journal of Thermophysics (2020) 41:166 Page 9 of 17 166

Table 2  Experimental and computed surface tensions for the aqueous solutions of SLES, ethanol, ace-
tonitrile, 1-propanol, and 2-propanol at T = 298.15 K and P = 1 atm
C/mol·m−3 σexp/mN·m−1 σcal/mN·m−1 C/mol·m−3 σexp/mN·m−1 σcal/mN·m−1

SLES 85.262 65.41 65.41

0.173 56.74 53.27 97.442 65.29 65.25
0.346 49.38 45.94 109.622 65.00 65.11
0.520 41.05 41.05 121.803 64.79 64.98
0.693 34.65 37.34 1-Propanol
0.866 31.38 – 8.320 67.08 68.49
1.040 30.50 – 16.64 67.07 67.61
1.213 30.97 – 24.96 67.02 67.02
1.387 30.73 – 33.28 66.66 66.56
Ethanol 41.60 66.28 66.18
2.170 69.21 69.21 49.92 65.89 65.86
10.853 67.93 67.93 66.56 64.88 65.33
21.706 67.39 67.27 83.20 63.71 64.89
32.559 67.00 66.84 2-Propanol
43.412 66.56 66.53 1.663 68.88 70.01
54.265 66.16 66.28 3.327 68.77 69.42
65.118 66.00 66.06 4.991 68.77 68.99
75.971 65.78 65.88 6.655 68.64 68.63
86.824 65.72 65.72 8.319 68.3 68.32
97.677 65.72 65.57 12.47 67.71 67.71
Acetonitrile 16.63 66.89 67.21
3.654 68.13 68.48 24.95 66.15 66.44
12.180 67.46 67.46 33.27 65.64 65.84
24.360 66.83 66.78 41.59 65.11 65.34
36.540 66.58 66.36 49.91 64.91 64.91
48.721 66.28 66.05 66.55 64.20 64.19
60.901 66.13 65.79 83.19 63.67 63.59
73.081 65.51 65.59

surface tension was considered as an average of three measurements. Table 2 pre-

sents the experimental surface tensions and Fig. 2 depicts the surface tension of the
aqueous solution of SLES in terms of concentration.
Similar to other anionic surfactants, the surface tension decreases as the concen-
tration of SLES increases until the concentration of SLES reaches critical micelle
concentration (CMC). Accordingly, the micelles of SLES can form when the

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166 Page 10 of 17 International Journal of Thermophysics (2020) 41:166

Fig. 2  Experimental and reproduced surface tensions for the aqueous solution of SLES at the tempera-
ture of 298.15 K

concentration of SLES reaches CMC. At the concentrations higher than the CMC,
the surface tension of the aqueous solution of SLES demonstrates no change. CMC
values are determined by the point of intersection of the two lines passing through
the experimental data (Fig. 2). Based on surface tension measurements, the CMC
value regarding pure SLES was 0.867 mol·m−3, which is in good agreement with the
previous reported data (0.82 mol·m−3) [13].
In the present study, a theoretical model was presented to reproduce the surface
tension of the aqueous solutions of SLES and additives, including ethanol, acetoni-
trile, 1-propanol, and 2-propanol. The proposed model was based on the equality
of chemical potentials in the liquid phase and the surface layer. The model is only
applicable for the concentrations lower than the CMC. The fitting parameters (i.e., a ,
b, and 𝜔1 ) of the presented model were regressed based on the surface tension data.
Table 3 summarizes these three parameters for each pure substance. Equation 16 was

Table 3  The determined Chemical Parameter b/m3·mol−1 a

molar area, surface-to-solution ω/105 m2·mol−1
distribution constant, and
interactions for the aqueous SLES 1.418 10.2872 − 0.245
solutions of pure SLES, ethanol,
acetonitrile, 1-propanol, and Ethanol 3.8 0.0245 − 0.94
2-propanol by using the model Acetonitrile 7.762 0.9087 − 0.6207
1-Propanol 2.789 0.05 719 − 2.597
2-Propanol 2.110 0.03 885 − 2.788

13
International Journal of Thermophysics (2020) 41:166 Page 11 of 17 166

used to determine 𝜔0 according to ­Vb and ­Vc values, which are 18.069 cm3·mol−1
and 57.1 cm3·mol−1, respectively [21].
The surface pressure (π) and surface coverage (θ) can be calculated accord-
ing to Eqs. 14 and 15. There is a good agreement with the measured surface
tensions so that the presented model can be used for successfully reproducing
the variations of the surface tension in terms of species concentrations with the
­AADγ of 1.45 %. Table 3 demonstrates that the surface-to-solution distribution
constant (b) of the applied additives is extremely lower than the one for SLES,
suggesting that additives represent no high surface activity when compared to
SLES.
The aqueous solutions of (SLES + additives) were prepared to study the influ-
ence of additives on the interfacial behavior of SLES. The concentration of addi-
tives was 10, 20, 30, and 40 wt %. First, the surface tension of the prepared aque-
ous solutions was measured as explained in the previous section. Table 4 presents
the experimental surface tension data.
The surface tension measurements were then used to determine the CMC
of the prepared mixed solutions. The measured CMC values are reported in
Table 5. As shown in Table 5, the CMC of SLES increases in the presence of the
employed additives. Furthermore, the CMC of SLES increases by increasing the
percentage of additives. It should be noted that an increase in the concentration of
additives leads to an increase in the hydrophobicity of the liquid phase. When a
single surfactant is present in an aqueous solution, the hydrophobic tail group of
this surfactant tends to adsorb at the surface layer. In the presence of an additive,
more hydrophobic tails of SLES can remain in the liquid phase due to an increase
in the hydrophobicity of the aqueous solution. On the other hand, the influence
of hydrophobicity due to the hydrophobic tail of surfactants is considered as the
main driving force of micelle formation [22]. Therefore, the CMC of the SLES
solution increases when it is used in the presence of additives.
Additionally, the presented model was applied to the aqueous solutions of
(SLES + additives). As mentioned in the modeling section, Eqs. 18–20 can be
used for describing the aqueous mixtures of SLES and additives. The previously
listed parameters (Table 3) were used regarding these equations. The comparison
of the predicted and measured surface tensions (Table 4 and Figs. 3, 4, 5) con-
firms the accuracy of the proposed model. In addition, this model can be utilized
for the simultaneous prediction of the surface pressure (π) or surface tension (γ)
and the surface coverage (θ) regarding (SLES + additive) mixtures. The surface
coverage in terms of SLES concentrations is plotted in Figs. 6, 7, 8.
The obtained results confirmed that the surface coverage of SLES decreases
when it is applied in the presence of additives. Furthermore, adding an additive
to an aqueous solution of a surfactant results in increasing the hydrophobicity
of the liquid phase. Accordingly, more hydrophobic tails of SLES can remain in
the liquid phase. Such an effect can decrease the absorption of the molecules of
SLES in the surface layer thus the surface coverage of SLES in the presence of
additives is less than the one in the absence of additives [22]. Therefore, the pre-
sented model can be used for accurately predicting the effect of additives on the
interfacial behavior of aqueous solutions.

13
 Table 4  Experimental and computed surface tensions for the aqueous solutions of SLES in the presence of different concentrations of additives at T = 298.15 K and
166

P = 1 atm
C/mol·m−3 σexp/mN·m−1 σcal/mN·m−1 C/mol·m−3 σexp/mN·m−1 σcal/mN·m−3 C/mol·m−3 σexp/mN·m−1 σcal/mN·m−1

13
(10 wt % Ethanol + 90 wt % SLES) 0.485 44.27 45.39 0.416 45.80 47.18
0.156 61.49 56.98 0.728 37.75 40.40 0.624 37.82 42.35
Page 12 of 17

0.312 49.88 50.35 0.971 30.59 – 0.832 34.13 38.67

0.624 43.03 42.35 1.214 30.55 – 1.040 32.49 –
0.936 33.72 – 1.456 30.64 – 1.248 31.09 –
1.248 32.63 – 1.699 30.96 – 1.456 30.84 –
1.560 32.48 – (40 wt % Acetonitrile + 60 wt % SLES) 1.664 30.41 –
1.872 32.89 – 0.104 63.50 60.15 (10 wt % 2-Propanol + 90 wt % SLES)
(20 wt % Ethanol +80 wt % SLES) 0.208 54.82 54.40 0.156 59.52 56.97
0.139 59.12 57.95 0.416 45.52 47.18 0.3121 49.67 50.35
0.277 50.02 51.57 0.624 40.07 42.35 0.624 37.28 42.35
0.555 40.78 43.79 0.832 35.09 38.67 0.936 29.90 –
0.832 35.46 38.67 1.040 31.75 – 1.248 30.13 –
0.971 33.69 – 1.248 31.63 – 1.560 29.93 –
1.109 32.90 – 1.456 31.53 – 1.872 30.70 –
1.387 32.80 – (10 wt % 1-Propanol + 90 wt % SLES) 2.184 31.29 –
1.664 32.82 – 0.156 57.51 56.98 (20 wt % 2-Propanol + 80 wt % SLES)
International Journal of Thermophysics

(30 wt % Ethanol +70 wt % SLES) 0.312 48.64 50.35 0.139 60.47 57.95
0.121 63.01 59.00 0.624 39.32 42.35 0.277 53.93 51.57
0.243 54.85 52.92 0.936 31.83 – 0.555 42.30 43.79
0.485 42.08 45.39 1.248 30.90 – 0.832 35.16 38.67
0.728 33.30 40.40 1.560 30.65 – 1.109 30.29 –
(2020) 41:166

0.971 31.14 – 1.872 30.11 – 1.387 30.02 –

 Table 4  (continued)
C/mol·m−3 σexp/mN·m−1 σcal/mN·m−1 C/mol·m−3 σexp/mN·m−1 σcal/mN·m−3 C/mol·m−3 σexp/mN·m−1 σcal/mN·m−1

1.214 31.02 – 2.184 30.72 – 1.664 29.89 –

1.456 31.27 – (20 wt % 1-Propanol + 80 wt % SLES) 1.942 30.00 –
(10 wt % Acetonitrile + 90 wt % SLES) 0.139 61.37 57.95 (30 wt % 2-Propanol + 70 wt % SLES)
0.156 61.77 56.98 0.277 52.00 51.57 0.121 62.37 59.00
0.312 49.64 50.35 0.555 39.74 43.79 0.243 50.52 52.91
0.624 40.05 42.35 0.832 35.72 38.67 0.485 44.57 45.39
0.936 37.65 – 1.109 31.85 – 0.728 37.46 40.40
International Journal of Thermophysics

1.248 36.92 – 1.387 31.76 – 0.971 33.60 –

1.560 35.05 – 1.664 31.85 – 1.214 31.94 –
1.872 35.69 – 1.942 31.86 – 1.456 31.98 –
(20 wt % Acetonitrile + 80 wt % SLES) (30 wt % 1-Propanol + 70 wt % SLES) 1.699 31.87 –
0.139 62.65 57.95 0.121 61.88 59.01 (40 wt %2-Propanol + 60 wt % SLES)
(2020) 41:166

0.277 54.68 51.58 0.243 54.51 52.92 0.104 64.02 60.13

0.555 45.14 43.79 0.485 43.37 45.39 0.208 55.91 54.38
0.832 39.45 38.67 0.728 40.14 40.40 0.416 46.03 47.17
0.971 37.11 – 0.971 36.39 36.63 0.624 40.42 42.34
1.109 36.40 – 1.214 33.29 – 0.832 36.22 38.67
1.387 36.31 – 1.456 32.79 – 1.040 31.80 –
1.664 35.49 – 1.699 32.31 – 1.248 30.70 –
1.942 35.27 – 1.942 32.12 – 1.456 30.67 –
(30 wt % Acetonitrile + 70 wt % SLES) (40 wt % 1-Propanol + 60 wt % SLES) 1.664 31.06 –
0.121 63.17 59.01 0.104 64.68 60.15
Page 13 of 17

0.243 55.14 52.92 0.208 56.22 54.40

166

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166 Page 14 of 17 International Journal of Thermophysics (2020) 41:166

Table 5  The variation of the CMC (mol·m−3) value for the SLES solution in the presence of different
additives at the temperature of 298.15 K and P = 1 atm
Weight percent SLES SLES + Ethanol SLES + Ace- SLES + 1-Pro- SLES + 2-Pro-
(wt %) of additives tonitrile panol panol

0 0.843 0.843 0.843 0.843 0.843

10 – 0.875 0.850 0.906 0.907
20 – 0.917 0.923 1.012 1.053
30 – 0.971 0.983 1.100 1.102
40 – 1.081 1.040 1.248 1.187

70
Experimental
60
model
50

40
σ/mN/m

30

20

10

0
0.1 1 10
c SLES /mol/m3

Fig. 3  Experimental and predicted surface tensions of SLES solution (σ) in terms of SLES concentration
at T = 298.15 K in presence of 20 wt % Ethanol

5 Conclusions

The present study measured the surface tensions and the critical micelle concen-
tration (CMC) of the single and mixed aqueous solutions of sodium lauryl ether
sulfate (SLES), ethanol, acetonitrile, 1-propanol and 2-propanol at T = 298.15 K
and various species concentrations. Furthermore, a theoretical thermodynamic
model was presented for explaining the observed surface phenomena. The results
revealed that although an increase in SLES concentration leads to higher sur-
face coverage, the presence of other additives can decrease the surface coverage
of SLES while increasing the CMC of the mixtures. In other words, the results
indicated that adding the above-mentioned chemicals to the aqueous solution of
SLES anionic surfactant leads to an increase in the hydrophobicity of SLES in
the liquid phase. This may decrease the absorption of the molecules of SLES in
the surface layer, leading to a reduction in the surface coverage of SLES in the

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International Journal of Thermophysics (2020) 41:166 Page 15 of 17 166

70
Experimental
60
Model
50
σ/mN/m

40

30

20

10

0
0.1 1 10
c SLES /mol/m3

Fig. 4  Experimental and predicted surface tensions of SLES solution (σ) in terms of SLES concentration
at T = 298.15 K in presence of 40 wt % Acetonitrile

70
Experimental
60
Model
50

40
σ/mN/m

30

20

10

0
0.1 1 10
c SLES /mol/m3

Fig. 5  Experimental and predicted surface tensions of SLES solution (σ) in terms of SLES concentration
at T = 298.15 K in presence of 30 wt % 1-Propanol

presence of the above-mentioned additives. Therefore, the presented thermody-

namic model can be used for the accurate prediction of the surface tension and

13
166 Page 16 of 17 International Journal of Thermophysics (2020) 41:166

0.8

0.7

0.6

0.5

0.4

0.3

0.2 Pure Texapon

0.1
20 wt% Ethanol
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
c SLES /mol/m3

Fig. 6  Surface coverage (θ) versus SLES concentration for the aqueous solution of pure SLES (Texapon)
and aqueous solution of SLES in the presence of 20 wt % Ethanol at T = 298.15 K

0.8

0.7

0.6

0.5

0.4

0.3

0.2
Pure Texapon
0.1
40 wt% Acetonitrile
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
c SLES /mol/m3

Fig. 7  Surface coverage (θ) versus SLES concentration for the aqueous solution of pure SLES (Texapon)
and aqueous solution of SLES in the presence of 40 wt % Acetonitrile at T = 298.15 K

surface coverage of the SLES surfactant in the presence of different additives in

mixtures. Eventually, the presented experimental and theoretical investigations in
the present study are quite important for evaluating the surface properties of the
widely used SLES mixtures in detergent and chemical industries.

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International Journal of Thermophysics (2020) 41:166 Page 17 of 17 166

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2 Pure Texapon

0.1
30 wt% 1-Propanol
0
0 0.2 0.4 0.6 0.8 1 1.2
c SLES /mol/m3

Fig. 8  Surface coverage (θ) versus SLES concentration for the aqueous solution of pure SLES (Texapon)
and aqueous solution of SLES in the presence of 30 wt % 1-Propanol at T = 298.15 K

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