J. Chem.

Thermodynamics 101 (2016) 236–244

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Effect of temperature and composition on the surface tension and

surface properties of binary mixtures containing DMSO and short chain
alcohols
Ahmad Bagheri ⇑, Mostafa Fazli, Malihe Bakhshaei
Department of Chemistry, Semnan University, P.O. Box 35131-19111, Semnan, Iran

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

Article history: Surface tension of binary mixtures of methanol, ethanol and isopropanol with DMSO (dimethyl sulfoxide)
Received 20 January 2016 was measured over the whole range of composition at atmospheric pressure of 82.5 kPa within the tem-
Received in revised form 28 May 2016 peratures between (298.15 and 328.15) K. The experimental measurements were used to calculate in sur-
Accepted 9 June 2016
face tension deviations (Dr). The sign of Dr for all temperatures is negative (except of methanol/DMSO
Available online 13 June 2016
system) because of the factors of hydrogen bonding and dipole–dipole interactions in the DMSO-alcohol
systems. Surface tension values of the binary systems were correlated with FLW, MS, RK and LWW mod-
Keywords:
els. The mean standard deviation obtained from the comparison of experimental and calculated surface
Surface tension
Correlation
tension values for binary systems with three models (FLW, MS and RK) at various temperatures is less
Surface enthalpy than 0.83. Also, the results of the LWW model were used to account for the interaction energy between
Lyophobicity alcohols and DMSO in binary mixtures. The temperature dependence of r (surface tension) at fixed com-
position of solutions was used to estimate surface enthalpy, Hs, and surface entropy, Ss. The results
obtained show that the values of the thermodynamic parameters for alcohol/DMSO mixtures decrease
with increasing alkyl chain length of alcohol. Finally, the results are discussed in terms of surface mole
fraction and lyophobicity using the extended Langmuir (EL) isotherm.
Ó 2016 Elsevier Ltd.

1. Introduction contain polar or polar aprotic solvents [1–3,11,12]. The experimen-

Among the various experimental methods, surface tension is
one of the most powerful techniques that provide information
about surfaces and intermolecular interaction. The study of the
surface properties in liquid mixtures is of great interest from both
scientific and industrial points of view [1–3].
Dimethyl sulfoxide (DMSO) is a non-aqueous dipolar aprotic
solvent used in pharmaceuticals, surface cleaners, extraction, elec-
trochemistry and as a solvent for polymers. As pure solvent, DMSO
has a large dipole moment and high dielectric constant (the rela-
tive dielectric constant e = 46.50 and dipole moment l = 4.06 D
at 298.15 K) [4–6].
Also, alcohols are considered to be a water-like solvent in terms
of hydrogen-bonding ability and are an important solvent due to
their use in the chemical, pharmaceutical, fuel cell, cosmetic indus-
tries and others [7–10].
This study is a continuation of our systematic experimental
research on surface properties of binary liquid mixtures that
⇑ Corresponding author.
E-mail address: abagheri@semnan.ac.ir (A. Bagheri).
tal values of surface tension of the binary systems consisting of
DMSO with methanol, ethanol and isopropanol were determined
over the whole range of composition at (298.15, 308.15, 318.15
and 328.15) K.
After surveying the literature, a number of research studies
have been located on the surface tensions of DMSO with alkanols
binary mixtures at various temperatures. However, no surface ten-
sion values were previously reported for DMSO with isopropanol at
different temperatures and DMSO with methanol and ethanol at
(308.15, 318.15 and 328.15) K [1,2,13–15].
After experimental measurements, the data obtained were
analysed using various methods. In the first section, the concentra-
tion dependence of the surface tension of binary DMSO-alcohol
mixtures at various temperatures are correlated using Fu et al.
(FLW) [16], the Myers-Scott (MS) [17] and Redlich-Kister (RK)
[18] and Li et al. (LWW) equations, and then in a new approach,
the effect of alcohol structure on the interaction energy values
(between alcohols and DMSO) is discussed in the binary systems
[19,20].
In the second section of this work, by employing the measured
surface tensions at various temperatures, the thermodynamic

http://dx.doi.org/10.1016/j.jct.2016.06.004
0021-9614/Ó 2016 Elsevier Ltd.
 A. Bagheri et al. / J. Chem. Thermodynamics 101 (2016) 236–244 237

properties of the surface (Hs and Ss) have been obtained. Finally, a
Langmuir type isotherm model (or the extended Langmuir (EL)) is
employed to determine the surface concentrations from the
knowledge of the bulk mole fractions. The results provide informa-
tion on the molecular interactions between the unlike molecules
that exist at the surface and the bulk at various temperatures
[20,21].
2. Experimental
2.1. Materials
All compounds were purchased from Merck and used without
any further purification. Purity of each compound was ascertained
by gas chromatography (GC type Agilent 7820A Agilent Technolo-
gies). The water mass fraction of the all components was deter-
mined by Karl Fisher (K.F.) titration, and it was found to be less
than 0.0008 for DMSO and less than 0.004 for alcohols. Chemicals
were kept in dark bottles. The detailed information of the materials
used in the experiment is listed in Table 1.
The purity of components was checked by comparing the
measured surface tension with those reported in the literature
[13–15,22–29]. The resultant values are in good agreement with
values found in the literature and reported in Table 2 [14].
Bi-distilled water has been used for checking the performance of
the tensiometer instrument in previous publication [25].
2.2. Apparatus and procedure
The surface tension of each sample liquid (pure or mixture) was
measured using the platinum-iridium ring method with a PC con-
trolled KSV Sigma 701 tensiometer. The ring was thoroughly
cleaned and flamed before each measurement. The measurements
were automatically corrected to the actual values by means of the
Huh and Mason compensation for interface distortion [30,31]. The
use of boiling distilled water can be a good (alternative) procedure
(for checking the performance of the instrument). The uncertainty
in the calculated surface tensions (the mean value from 7 points)
was estimated to be ±0.04 mN
m1. The measurements were car-
ried in the temperature range from 298.15 K to 328.15 K and at
pressure of 82.5 kPa. The sample under measurement was kept
thermostatted in a double-jacketed glass cell by means of a water
bath, using a LAUDA circulator (model ECO RE415) equipped with a
Pt100 probe, immersed in solution, and able to control the temper-
ature within ±0.01 K.
The binary mixtures were prepared by mass using a Sartorius
analytical balance (model BP 121S, accurate to ±0.1 mg). The stan-
dard uncertainty of the mole fractions is ±1.000  103.
3. Results and discussion
3.1. Correlation of surface tension and concentration in binary
mixtures

The concentration dependence of the surface tension of mix-

Table 1
Specification of the chemicals employed in this work.
tures can be represented in terms of the surface tension deviation,
Dr, defined as:
Component CAS Supplier Purity (mass Water content
number fraction) (mass fraction) X
n

Supplier GC Supplier K.F. Dr ¼ r  xi ri ð1Þ

a
i¼1
DMSO 67-8-5 Merck >0.995 0.995 <0.001 0.0008
Methanol 67-56-1 Merck >0.995 0.996 60.0002 0.0002
Ethanol 64-17-5 Merck >0.995 0.997 <0.0005 0.0003
where r is the surface tension of the mixture, and ri is the surface
Isopropanol 67-63-0 Merck >0.99 0.990 <0.005 0.0035 tension of the pure component I at the same temperature and pres-
a
sure of the mixture, xi is the mole fraction of the component I and n
Dimethyl sulfoxide.
is the number of components.
A few empirical and thermodynamic-based equations are avail-
able to correlate the surface tension; some of them have recently
Table 2 proposed and are well founded on a thermodynamic basis. Fu
Comparison of experimental surface tension, r, of pure components with literature et al. (FLW) proposed a two-parameter equation to correlate the
values at atmospheric pressure of 82.5 kPa within the temperatures between (298.15 surface tension with the composition in the binary systems which
and 328.15) K.a
is based on the local composition concept due to the Wilson equa-
Component T/K r/(mN
m1) tion [16]. Another surface tension correlation was proposed by Li
Exptl. Lit. et al. (LWW) for liquid mixtures, which is based on the Wilson
equation for the excess Gibbs energy [19,32]. Other empirical
DMSO 298.15 42.426 42.6514, 42.7822
308.15 41.295 40.9513, 41.6222 equation such as Myers-Scott (MS) has been applied for the corre-
318.15 40.173 40.4123 lation of binary surface tension values [17]. The relevant equations
328.15 39.081 39.3823 for all the models for surface tension (or the surface tension devi-
Methanol 298.15 22.241 22.2013, 22.1824 ation) correlation, in this work, are summarized in Table 3.
308.15 21.413 21.5225, 21.3526 In Table 4, the measured surface tension is presented for binary
318.15 20.530 20.6125, 20.3324
systems over the range T = (298.15–323.15) K at intervals of 10 K
328.15 19.541 19.3924
as a function of mole fraction.
Ethanol 298.15 21.658 21.7427, 21.8028
Figs. 1–3 show the behaviour of surface tension of alcohol in
308.15 21.011 21.0425, 21.0329
318.15 20.189 20.2225
DMSO at various temperatures. In all systems, the surface tension,
328.15 19.235 19.3814 r, decreased with increasing alcohol concentration. This trend is
Isopropanol 298.15 21.146 21.2225
non-linear, with the change in surface tension caused by a given
308.15 20.286 20.2325, 20.2015 change in alcohol mole fraction being greater at low mole fraction
318.15 19.525 19.4715 than at high mole fraction. On the other hand, as discussed above,
328.15 18.512 18.414 DMSO and alcohol interact strongly and mixtures form non-ideal
Water 298.15 72.05 72.0125 solutions particularly in the low concentration regime. This beha-
a
Standard uncertainties u are u(T) = 0.01 K, u(P) = 10 kPa, u(x) = 0.001 and the
viour is typically explained by a difference in distribution of mole-
combined expanded uncertainty Uc is Uc(r) = 0.114 mN
m1 (0.95 level of cules between the surface and the bulk of the liquid. In a
confidence). characteristic case, the compound having a lower surface tension
238 A. Bagheri et al. / J. Chem. Thermodynamics 101 (2016) 236–244

Table 3
The empirical and thermodynamic-based models for correlation between surface tension (or the surface tension deviation) and concentration in binary mixtures.

Model* Equation Adjustable coefficients Ref.

x1 r1 x2 r2 x1 x2 jr1 r2 j
FLW r¼ x1 þx2 f 12
þ x2 þx1 f 21
 ðx1 þx2 f 12 Þðx2 þx1 f 21 Þ
f 12 and f 21 [16]
 
MS Dr ¼ x1 x2 B0 þB1 ðx2 x1 Þ B0 , B1, C 1 and C 2 [17]
1þC 1 ðx2 x1 ÞþC 2 ðx2 x1 Þ2

RK Dr ¼ x1 x2 ðA þ Bðx2  x1 Þ þ Cðx2  x1 Þ2 þ Dðx2  x1 Þ3 Þ A, B, C and D [18]

  h i  
LWW Dr ¼  x2xþx
1 x2 RT @ K21
1  K121 K21 and @@A K21 [19]
1 K21 @A T;p;x T;p;x

*
The details of the models were described in previous work [3,11,12].

Table 4 45
Surface tension, r, of alcohol mixed with DMSO at pressure of 82.5 kPa within the
temperatures between (298.15 and 328.15) K and mole fraction of alcohols (x2).a
40
r/(mN
m1)
T/K
35
Methanol x2 298.15 308.15 318.15 328.15

σ/(mN.m-1)
0.077 41.308 40.204 39.147 38.060
0.154 40.028 38.951 37.906 36.838 30
0.231 38.591 37.536 36.578 35.549
0.308 37.103 36.158 35.204 34.251
25
0.384 35.598 34.689 33.784 32.839
0.462 34.069 33.178 32.314 31.452
0.538 32.464 31.625 30.794 29.964 20
0.615 30.844 30.027 29.219 28.413
0.693 29.196 28.384 27.558 26.794
0.769 27.497 26.693 25.837 24.956 15
0.846 25.767 24.892 24.203 23.313 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.900 24.556 23.670 22.885 21.943 x2
Ethanol 0.087 39.250 38.319 37.348 36.366
0.174 36.687 35.751 34.879 33.987 Fig. 1. Experimental surface tension, r, against mole fraction, x2, at various
0.261 34.396 33.602 32.691 31.871 temperatures: (d) 298.15 K, (h) 308.15 K, (N) 318.15 K and (*) 328.15 K, for
0.348 32.294 31.504 30.730 29.993 methanol (2)/DMSO (1). The continuous dashed curves represent the correlation
0.435 30.479 29.708 28.954 28.220 with the FLW equation.
0.522 28.843 28.076 27.330 26.611
0.609 27.339 26.580 25.833 25.211
0.696 26.035 25.223 24.442 23.636 45
0.783 24.633 23.908 23.140 22.358
0.870 23.398 22.699 21.913 21.075
40
Isopropanol 0.044 39.171 38.581 37.896 36.909
0.085 36.422 35.880 34.989 34.123
0.157 33.827 32.833 32.049 31.153
35
0.245 30.887 30.212 29.546 28.386
σ/(mN.m-1)

0.338 28.564 27.701 27.016 25.999

0.441 26.667 25.875 25.191 24.104 30
0.537 25.154 24.461 23.866 22.793
0.619 24.194 23.394 22.812 21.738
0.676 23.185 22.836 22.059 21.079 25
0.719 23.033 22.477 21.666 20.722
0.751 22.842 22.206 21.427 20.449
0.860 22.002 21.209 20.511 19.586 20
a
Standard uncertainties u are u(T) = 0.01 K, u(P) = 10 kPa, u(x) = 0.001 and the
combined expanded uncertainty Uc(r) = 0.114 mN
m1 (0.95 level of confidence). 15
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x2
(alcohol) is expelled from the bulk to the liquid–vapour interface
due to the attractive forces between solvent molecules [1,2,20]. Fig. 2. Experimental surface tension, r, against mole fraction, x2, at various
Over the whole composition range, the values of Dr for the temperatures: (d) 298.15 K, (h) 308.15 K, (N) 318.15 K and (*) 328.15 K, for ethanol
(2)/DMSO (1). The continuous dashed curves represent the correlation with the
binary mixtures of ethanol and isopropanol with DMSO are FLW equation.
negative but the values of Dr for the methanol/DMSO mixtures
are positive. The values of jDrj for mixtures of alcohol (ethanol
or isopropanol)/DMSO decrease with increasing temperature and (2)/DMSO (1) indicate that the components with the strongest
the alkyl chain length of alcohol (see Fig. 4). molecular interactions in each binary mixture settle down in the
In the binary mixtures of DMSO with ethanol and isopropanol, bulk liquid phase instead of interacting in the surface phase
the surface tension deviation (Dr) values increase with increase between liquid and vapour phases, moving the curves to the rich
in the difference of surface tension values of pure components, region of these compounds.
pass through a minimum at x1  0.25–0.375 (in isopropanol However, there is a different trend for the methanol/DMSO mix-
(2)/DMSO (1)) and x2  0.33–0.45 (in ethanol (2)/DMSO (1)). The ture, the strong interactions between DMSO and methanol
asymmetry in the curves of isopropanol (2)/DMSO (1) and ethanol decrease the tendency of methanol to adsorb at the liquid–vapour
 A. Bagheri et al. / J. Chem. Thermodynamics 101 (2016) 236–244 239

45 methanol molecules form hydrogen-bonded complexes with

DMSO, in which these interactions partially replace methanol–
40
methanol hydrogen bonding [33,36–39].
In Figs. 5–7 we have plotted the experimental and fitted values
of surface tension of the binary systems of alcohol/DMSO as a func-
35 tion of the composition with FLW, MS, RK and LWW models:
σ/(mN.m-1)

In Table 5, the adjusted coefficients of the equations used to

30 correlate the binary data are listed as well as the respective stan-
dard deviations of the fittings.
The adjustable parameters in LWW model (Table 3) represent
25
the following:
     
20 U  U ii @ Kij Kij @ðU ij  U ii Þ
Kij ¼ exp  ij ; ¼ ð2Þ
RT @A T;P;X RT @A T;P;X

15 In the preceding relations, UijUii is the difference in the inter-

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
action energy between molecular pair ij, and the derivative
x2
½@ðU ij  U ii Þ=@AT;P;x reflects the energy change with the increase
Fig. 3. Experimental surface tension, r, against mole fraction, x2, at various in surface area [19,20]. The correlation results using the LWW
temperatures: (d) 298.15 K, (h) 308.15 K, (N) 318.15 K and (*) 328.15 K, for model and the relevant results for the binary systems are listed
isopropanol (2)/DMSO (1). The continuous dashed curves represent the correlation in Table 6.
with the FLW equation.

45
1.5
43
0.5
40
-0.5
38
-1.5
Δσ/(mN.m-1)

σ/(mN.m )

35
-1

-2.5
33
-3.5 30

-4.5 28

-5.5 25

-6.5 23

-7.5 20
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x2 x2

Fig. 4. Plot of surface tension deviation, Dr, against mole fraction at 308.15 K. The Fig. 5. Plot of surface tension, r, against mole fraction at 298.15 K. The symbols
symbols refer to the experimental values for the alcohol (2)/DMSO (1) mixture: (N) refer to the experimental data for alcohol (2)/DMSO (1) mixture: (d) methanol, (N)
methanol, (j) ethanol and (d) isopropanol. ethanol and (s) isopropanol. The continuous dotted curves represent the correla-
tion with the FLW equation.

interface, which is in turn responsible for the positive Dr for

the methanol/DMSO system. According to results of the
1.4
ERAS (extended real associated solution) model, the value of
cross-association constant between alcohol and DMSO (Kalcohol-DMSO)
1.2
was reduced from methanol to 1-pentanol at 298.15 K due to strong
reduction of hydrogen bonding [33–35]:
1.0
Δσ/(mN.m )
-1

0.8
K methanol-DMSO ð¼ 4:3Þ > K ethanol-DMSO ð¼ 1:5Þ > K isopropanol-DMSO ð¼ 1:4Þ
0.6
> K 1pentanol-DMSO ð¼ 1:2Þ
0.4
The two factors (surface tension and hydrogen bonding) are
antagonistic in migration of methanol molecules from the bulk to
0.2
interface. This is due to the hydrogen-bonding factor between
methanol and DMSO, the more abundant methanol prefers the 0.0
bulk liquid phase (according to the results of ERAS model), but 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
due to the surface tension factor it prefers the interface. From x2
the experimental results, it appears that the hydrogen-bonding
factor is more important than the surface tension factor. The strong Fig. 6. Plot of surface tension deviation, Dr, against mole fraction for methanol (2)/
DMSO (1) system. The symbols refer to the experimental data at various
interactions between DMSO and methanol decrease the tendency temperatures: (d) 298.15 K, (s) 308.15 K, (N) 318.15 K and (j) 328.15 K. The
of methanol to adsorb at the liquid–vapour interface. Numerous continuous dotted curves represent the correlation with MS equation and the solid
studies reported in the literature have provided evidence that curves represent the correlation with the RK equation.
240 A. Bagheri et al. / J. Chem. Thermodynamics 101 (2016) 236–244

the system isopropanol/DMSO, which is highly asymmetrical with

1.0
large values of Dr.
0.0

-1.0 3.2. The adjustable parameters of the LWW model for estimation of
interaction energy between components
-2.0
Δσ/(mN.m-1)

In this section, we present an application of the adjustable

-3.0
parameters of LWW model to explain the influence of alkyl chain
length of the alcohol on interaction energy values between
-4.0
components.
-5.0 As can be seen from LWW model, the surface tension deviation
(Dr) arises from the cross interaction between species i and j. For a
-6.0 non-ideal solution, the interaction energy between any two species
is not identical, i.e. Uii – Ujj – Uij.
-7.0 The physical significance of the LWW parameters can be under-
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 stood as follows: U21–U22 is directly related to the dimensionless
x2 parameter Kij via Eq. (2), which is used to account the local com-
position effect, and the term ½@ðU 12  U 11 Þ=@AT;P;x reflects the
Fig. 7. Plot of surface tension deviation, Dr, against mole fraction of alcohol (x2).
The symbols refer to the experimental data at 298.15 K: (d) methanol (2)/DMSO energy change with increase in surface area [19,20].
(1), (s) ethanol (2)/DMSO (1) and (N) isopropanol (2)/DMSO (1). The solid curves Table 6 summarizes U21–U22 and ½@ðU 21  U 22 Þ=@AT;P;x values
represent the correlation with MS equation, the continuous dotted curves represent that were obtained from LWW model. Since the U21–U22, depends
the correlation with RK equation and the continuous dashed curves represent the
mainly on variation in intermolecular interactions between two
correlation with the LWW equation.
components into contact, if interaction energy between unlike
molecules (Ualcohol-DMSO or U21) are weaker than those existing
The standard deviations reported (S) in this table were com- between like molecules (Ualcohol-alcohol or U22), positive values of
puted by applying the following equation: U21–U22 will be observed at various temperatures (Uii or Uij is neg-
" #1=2 ative value).
XM
ðY exp  Y cal Þ2 Considering molecular structure of alcohols shows that the
S¼ ð3Þ strength of the hydrogen bond (the interaction energy) between
i¼1
MP
AOH group of alcohol and DMSO molecules decreases with
where Y stands for r or Dr, M and P are the number of data points increasing the alkyl chain length of alcohol (from methanol to iso-
and the number of adjustable parameters used for fitting the exper- propanol) at a given temperature. Therefore, at approximately con-
imental values in four models, respectively. stant value of Ualcohol-alcohol (25.1 kJ
mol1 at 298.15 K) [33–35],
The surface tension of the binary systems is well-correlated the values of Ualcohol-DMSO change as following: |Umethanol-DMSO| > |
using the FLW model (see Figs. 1–3). Uethanol-DMSO| > |Uisopropanol-DMSO| (see Fig. 8).
As expected the highest values of the mean standard deviation The data in Fig. 8 show the interaction energy between the alco-
(in four models) are obtained for the isopropanol/DMSO system hol and DMSO (U21) decreases with an increase of the alkyl chain
which has higher values of Dr and show markedly asymmetrical length of alcohol (from methanol to isopropanol at 298.15 K) due
variations of this property with the composition. to the weaker interaction between alcohol and DMSO. Fig. 8 (from
As can be seen from Figs. 5–7 and Table 5, the MS model corre- surface tension data) confirms the results obtained for the ERAS
lates the surface tension deviations of these systems well, even for model from the excess enthalpy (as noted above) [33–35].

Table 5
Adjustable parameter and standard deviation, S, of the models used to correlate surface tension with the composition for the binary systems at various temperatures.

Model A B C, D S/(mN m1) A B C, D S/(mN m1) A B C, D S/(mN m1)

c
Methanol/DMSO T = 298.15 K Ethanol/DMSO T = 298.15 K Isopropanol/DMSO T = 298.15 K
FLWa 0.074 0.883 0.016 0.426 0.979 0.040 0.245 1.920 0.201
MSb 3.848 17.714 4.973, 1.627 0.035 11.140 4.191 0.039, 0.124 0.043 24.413 11.612 0.977, 0.152 0.156
RK4 3.699 0.730 1.264, 1.538 0.013 11.139 4.667 1.650, 0.550 0.044 24.164 10.502 11.691, 15.315 0.170
Methanol/DMSO T = 308.15 K Ethanol/DMSO T = 308.15 K Isopropanol/DMSO T = 308.15 K
FLWa 0.057 0.855 0.042 0.490 0.925 0.029 0.264 1.767 0.119
MSb 4.258 20.744 5.161, 1.319 0.038 10.670 12.013 1.474, 0.391 0.031 23.267 26.280 1.700, 0.642 0.072
RK-4 4.227 0.306 0.334, 2.402 0.016 10.687 3.665 1.277, 0.854 0.032 23.213 13.226 9.097, 6.084 0.130
Methanol/DMSO T = 318.15 K Ethanol/DMSO T = 318.15 K Isopropanol/DMSO T = 318.15 K
FLWa 0.031 0.816 0.028 0.508 0.878 0.0006 0.289 1.643 0.190
MSb 4.915 21.569 4.554, 0.715 0.042 9.832 1.057 0.241, 0.028 0.0003 22.200 24.803 1.669, 0.612 0.087
RK-4 4.780 0.294 0.888, 1.298 0.029 9.829 3.415 1.164, 0.404 0.0009 22.130 12.511 8.341, 3.763 0.200
Methanol/DMSO T = 328.15 K Ethanol/DMSO T = 328.15 K Isopropanol/DMSO T = 328.15 K
FLWa 0.011 0.768 0.048 0.494 0.825 0.037 0.312 1.560 0.182
MSb 5.662 26.919 4.812, 0.148 0.048 8.549 10.471 1.613, 0.475 0.041 22.114 24.247 1.655, 0.613 0.058
RK-4 5.579 0.648 0.159, 2.185 0.040 8.533 3.369 1.460, 0.313 0.040 22.330 13.247 6.082, 1.428 0.172
a
The coefficients A and B correspond to f12 and f21, respectively.
b
The coefficients A, B, C and D correspond to B0, B1, C1 and C2, respectively.
c
Standard uncertainty in temperature, u(T) = 0.01 K.
 A. Bagheri et al. / J. Chem. Thermodynamics 101 (2016) 236–244 241

Table 6
Adjustable parameters and the obtained interaction energy values of the LWW model
for the binary systems of alcohol (2)/DMSO (1) at various temperatures. 42

a
Systems Parameters T/K
298.15 308.15 318.15 328.15 38

Methanol/ K21 0.4895 0.5859 0.7318 0.9713

DMSO  b 1.098 1.854 4.366 6.867
@ K21
 106 34

σ/(mN.m-1)
@A T;P;X

(U21–U22)/(J.mol1) 1770.77 1369.59 825.92 79.44

Ethanol/ K21 0.4209 0.4781 0.4864 0.4425
 b 30
DMSO @ K21 2.311 2.821 2.613 1.793
@A T;P;X  106
(U21–U22)/(J.mol1) 2145.19 1890.56 1906.22 2224.62
26
Isopropanol/ K21 0.2617 0.2718 0.2917 0.3052
DMSO  b 2.222 2.158 2.237 2.328
@ K21
@A T;P;X  106
22
(U21–U22)/(J.mol1) 3323.09 3337.24 3258.93 3237.66
a
Standard uncertainty in temperature, u(T) = 0.01 K.
b
Unit: m2. 18
295 300 305 310 315 320 325 330
T/K

Fig. 9. The temperature variation of the surface tension for the ethanol (2)/DMSO
(1) mixture at different mole fraction of ethanol. The solid lines are a guide for the
23.5
eyes, and the symbols refer to the experimental values: (d) 0.0, (j) 0.087, (N) 0.174,
(r) 0.261, (*) 0.348, (D) 0.435, (+) 0.522, () 0.609, (h) 0.696, () 0.783, (e) 0.870
and (s) 1.0.
23
 
@r
U21/(kJ.mol )

Hs ¼ r  T ¼ r þ TSs
-1

ð5Þ
22.5 @T p;x2

The obtained results were plotted in Figs. 10 and 11. As it was

22
21.5
0.5 1 1.5 2 2.5
n
Fig. 8. The interaction energy, U21, versus the numbether of carbon atoms, n, in
hydrocarbon chain of alcohol at 298.15 K.
3.3. Surface thermodynamic functions of binary mixtures
The temperature dependence of the surface tension is also
important for practical applications and modelling of the liquid
state. Basically, accurate experimental measurements of surface
tension as a function of temperature would provide the possibility
of accurate determination of surface thermodynamic functions. For
most binary mixtures at a given concentration, surface tension
shows a linear dependency with temperature, decreasing as tem-
perature increases (see Fig. 9, typically) [2,11,40,41].
shown in these figures, the patterns of both Hs and Ss are nearly
identical for all mixtures of DMSO with alcohols.
The obtained surface entropy (Ss) exhibits a rapid decrease in
the low concentrations of alcohols (until x2  0.5) and then it
3 3.5
remains almost constant for the rest of the solutions (see
Fig. 10). Recently, Bagheri et al. have reported the similar shape
of the Ss vs x2 curve for DMSO with long chain alcohols [2]. In these
mixtures, the alkyl group chain and the values of surface tension
deviation have a dominant effect on the surface thermodynamic
properties. It is interesting to note that where minimum values
of Ss and maximum surface tension deviations take place almost
at the same concentrations (x2  0.5).
0.12
0.11
0.10
Ss/(mN.m-1.K-1)

To investigate more closely the surface formation of the alcohol/

DMSO mixture, we apply some thermodynamic equations to the 0.09
experimental results to estimate the thermodynamic functions of
the surface formation.
0.08
The entropy of the surface formation) per unit surface area (or
specific surface entropy or SS/N
m1
K1) is evaluated by the fol-
lowing equation: 0.07
 
@r
Ss ¼  ð4Þ 0.06
@T p;x2
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Considering that the surface enthalpy is the sum of the surface x2
free energy required to extend the surface tension and the latent
Fig. 10. Plot of the surface entropy (SS) versus the mole fraction of alcohol (x2) in
heat (q) required to maintain isothermal conditions: HS = r + q, the temperature range from 298.15 K to 328.15 K for binary mixtures: (d)
the surface enthalpies per unit surface area have been calculated methanol (2)/DMSO (1) and (j) ethanol (2)/DMSO (1) and (N) isopropanol
[2,11,40,41]: (2)/DMSO (1).
242 A. Bagheri et al. / J. Chem. Thermodynamics 101 (2016) 236–244

80
21

75
18

70
15

π(mN.m-1)
65
HS/(mN.m-1)

12

60 9

55 6

50 3

45
40
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
x2
Fig. 11. Plot of the surface enthalpy (HS) versus the mole fraction of alcohol (x2) in
the temperature range from 298.15 K to 328.15 K for binary mixtures: (d)
methanol (2)/DMSO (1), (j) ethanol (2)/DMSO (1) and (N) isopropanol (2)/DMSO
(1).
As shown in Fig. 11, surface enthalpy (Hs) is positive and depends
remarkably both on the bulk composition and temperature.
3.4. The surface concentration of components in binary mixtures
The surface concentration is another parameter that produces
some useful information about the surface behaviour of mixtures.
An applied model (Extended Langmuir, EL) was reported, which
describes the surface tension of binary liquid mixtures as a func-
tion of the bulk composition [21].
If /2;s is the volume fraction of component 2 in the surface
phase, and /2 is the volume fraction of component 2 in the bulk
phase, then we define them in general as follow:
n2;s v 2
/2;s ¼ ¼ 1  /1;s
n1;s v 1 þ n2;s v 2
n2 v 2
/2 ¼ ¼ 1  /1
n1 v 1 þ n2 v 2
where ni is the number of moles of the ith component, v1 and v2 are
molar volume of the 1 and 2.
Briefly, this model considers the surface of a binary liquid mix-
ture as a thin but finite layer and the following expression was
developed for the relationship between /2;s and /2 :
b/2
/2;s ¼
1 þ ðb  1Þ/2
where the parameter b ¼ ð/2;s :/1 Þ=ð/1;s :/2 Þ is a measure of the
lyophobicity of 2 relative to 1. In this model, the surface tension
of non-ideal binary mixtures is given by:
r ¼ /1;s r1 þ /2;s r2  k/1;s /2;s p0
where r1 and r2 are the surface tensions of the pure components 1
and 2, respectively; p0 is the positive difference between them
|r1  r2| (1 is the component of higher surface tension); and k (or
a = k + 1) is a parameter that represents the effect of unlike-pair
interactions on the surface tension of the mixture. For comparisons
between different systems it is convenient to consider the surface
pressure p = r1  r, where r1 > r. Using Eq. (8) in Eq. (9) yields:
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x2
0.8 0.9 1.0
Fig. 12. Surface pressure, p, as a function of alcohol concentration (x2). The symbols
refer to the experimental surface pressure for binary mixtures at 298.15 K: (d)
methanol (2)/DMSO (1), (N) ethanol (2)/DMSO (1) and (j) isopropanol (2)/DMSO
(1) The solid curves were calculated using the EL model.
An iterative method has been used to derive the a and b param-
eters by inserting experimental values in Eq. (10) [19,20]. Table 7
lists the values of the adjustable parameters a and b obtained by
fitting Eq. (10) to the experimental results at 298.15 K.
Fig. 12 shows the experimental surface pressure values together
with the fitting curves obtained using the EL model for the
alcohol/DMSO systems.
The agreement between the experimental surface pressure val-
ues and those calculated from the EL model relation is found to be
satisfactory.
The b values for the mixtures of DMSO with ethanol and iso-
propanol are greater than unity and parameter k is zero (a  1),
which indicates that the compound prevalently adsorbed in both
cases is the alcohol. Both contributions tend to decrease the surface
tension of the mixture and the Dr–xalcohol curves show negative
ð6Þ minima. Also, Table 7 also indicates that the lyophobicity (b) in
the alcohol/DMSO mixtures increases with the alkyl chain length.
In the methanol/DMSO system, the fittings with EL model pro-
ð7Þ vide values of b = 1 and k > 0 (a = 1.37), this shows, the concentra-
tion of each compound being the same in bulk and surface phases
(due to the lyophobicity is not occurs) and the unlike-pair interac-
tions contribute to decrease the surface tension of the mixture.
In similar cases of methanol (2)/DMSO (1) (a positive maximum
in the Dr–x2 curve), several papers proposed that the molecules of
methanol because they are much smaller than those of DMSO
(v2/v1 = 0.57) and so, many more methanol molecules are needed
ð8Þ to cover the same area. Thus, despite the same concentration of
components at the interface, the contribution of the DMSO domi-
nates in the Dr–x2 representation [42–44].
The ‘‘non-ideality” of the surface tension of a given system is
also reflected using the surface layer concentration. A plot of the
surface mole fraction, x2,s, versus the bulk mole fraction, x2, gives
ð9Þ us the possibility of establishing the non-ideality of a given system
by observing the form of the corresponding curve (see Fig. 13). For
ideal systems, this curve tends to be a line very close to the one a
Table 7
Values of the parameters of a, b, p0 and DG0 for alcohol/DMSO mixture at 298.15 K.
Component a b p0 DG0/(kJ
mol1)

p0 b½b þ að/1 =/2 Þ Methanol 1.37 1.00 20.185 8262.48

p¼ 2
ð10Þ Ethanol 1.00 2.14 20.741 9416.34
½b þ ð/1 =/2 Þ Isopropanol 0.99 3.51 21.280 10690.4
 A. Bagheri et al. / J. Chem. Thermodynamics 101 (2016) 236–244 243

1.0 The standard Gibbs energy (DG0) can be used to evaluate the
spontaneity of an adsorption process. A negative DG0 indicates
0.9
the adsorption occurs spontaneous and is thermodynamically
0.8 stable, whereas the positive DG0 means this process is not favoured
0.7 and represents a non-spontaneous transfer [46].
The results in Table 7 show that the value of DG0 increases
0.6
with the increase of the alkyl chain length of the alcohol (due to
0.5 the lesser interaction between alcohol and DMSO). In the other
x2,s

words, these results indicate that the adsorption process becomes

0.4
more favourable with increasing alkyl chain length of the alcohol
0.3 from methanol to isopropanol.
0.2 As can be seen in Table 7, the agreement between the experi-
mental results and the values obtained from the Eq. (11) is
0.1
reasonable.
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 4. Conclusion
x2
In this paper, surface tension values for binary mixtures of alco-
Fig. 13. Surface mole fraction, x2,s, versus the bulk mole fraction (x2) of alcohol in
binary mixtures at 298.15 K: (N) methanol (2)/DMSO (1), (j) ethanol (2)/DMSO (1)
hol (methanol, ethanol and isopropanol) with DMSO, are reported
and (d) isopropanol (2)/DMSO (1). The solid curves are a guide for the eyes. over ranges of composition at various temperatures. In all systems,
the surface tension of mixtures decreases with increasing temper-
hypothetical ideal system would show, which corresponds to a 45° ature. The results of the present study show that by adding alcohol
to DMSO the surface tension decreases non-linearly and most sur-
slope straight line. In fact, the x2,s results are in full accordance
with b values [20,45]. face tension changes occur at a low concentration of alcohol. The
surface tension deviation, Dr, is positive for methanol/DMSO,
Fig. 14 shows the variation of x2,s  x2 with x2 for the
and is negative for DMSO with ethanol and isopropanol. This
alcohol/DMSO solutions. Generally, a basic trend is shown by
shows that the interaction is strong, namely formation of hydrogen
Fig. 14, x2,s  x2 value increases with increasing acid concentration
bonding between DMSO and methanol, and the interaction
and this process continues to reach a maximum, then with more
between DMSO with ethanol and isopropanol is weak. The exper-
increased alcohol concentration, x2,s  x2 decreases. The x2,s  x2
imental surface tension values for binary mixtures were correlated
values are positive in the whole composition range and increase
by four models (FLW, MS, RK and LWW) and the best results were
with increase of the length of the hydrocarbon chain of alcohols
obtained by the Myers-Scott (MS) model. In a new approach, we
(according to the previous discussion, it is expected that x2,s  x2
describe the alkyl chain length of alcohol on the interaction energy
for methanol/DMSO system is zero). Also, this figure confirms that
values in binary mixtures by using values of the surface tension.
the x2,s  x2 values increase with increasing difference of the polar-
The results obtained show the Ualcohol-DMSO value decreases with
ity of pure compounds.
increasing alkyl chain length of alcohol due to the lesser interac-
Finally, the standard Gibbs energy of adsorption, which reflects
tion between alcohol and DMSO at any temperature. The values
the energy required to move one molecule of solute from the bulk
of surface mole fraction of alcohol were calculated using the EL
to the surface, can be determined for the above systems by the EL
model. The extracted b values indicate the greater affinity of alco-
model using the equation [41]:
  hol for the surface, and this trend is amplified with the increase of
p0 abv 2 the alkyl chain length of the alcohol.
DG0 ¼ RT ln ð11Þ
v1
Acknowledgments
where a and b are the adjustable parameters of the EL model, v1 and
v2 are the molar volumes of the 1 and 2. The authors are grateful to Dr. S. Maryam Sajjadi who kindly
read the manuscript and made many helpful suggestions. Also,
0.35
we gratefully acknowledge the financial support received for this
research work from the Research Council of Semnan University.
0.30

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JCT 16-57