Prediction of the Surface Tension, Surface Concentration

and the Relative Gibbs Adsorption Isotherm of Non-ideal

Binary Liquid Mixtures
A. Bagheri

A. A. Rafati

A. Adeli Tajani

A. R. Afraz Borujeni

A. Hajian
Received: 25 February 2013 / Accepted: 18 June 2013 / Published online: 25 October 2013
Springer Science+Business Media New York 2013
Abstract Surface properties of binary mixtures of 1,2-ethanediol, 1,2-propanediol and
1,4-butanediol with acetonitrile have been measured by the surface tension method at
T = 298.15 K and atmospheric pressure. The surface tension has been predicted based on
the Suarez method. This method combines a model for the description of surface tension of
liquid mixtures by using the UNIFAC group contribution method for calculation of activity
coefcients. Also, the results have been discussed in terms of surface concentration and
lyophobicity using the extended Langmuir isotherm. The results provide information on
the molecular interactions between the unlike molecules that exist at the surface and the
bulk phase. Finally, experimental values of the surface tension have been correlated by the
RedlichKister and WangChen polynomial equations over the whole mole fraction range.
Keywords Surface tension Prediction Correlation Surface adsorption
UNIFAC
1 Introduction
Surface tension is an important physico-chemical property due to its inuence on several
natural phenomena, as well as industrial applications [1]. The surface tension of a liquid
mixture is not a simple a function of the surface tension of the pure components, because in
a mixture the composition of the interface is not the same as that of the bulk phase. The
deviation of the surface tension of a liquid mixture from linearity reects changes of
structure and cohesive forces during the mixing process [2]. At the interface there is
migration of the species having the lowest surface tension, or Gibbs energy per unit area, at
A. Bagheri (&) A. A. Tajani
Department of Chemistry, Semnan University, P.O. Box 35131-19111, Semnan, Iran
e-mail: bagheri.alm@gmail.com; abagheri@profs.semnan.ac.ir
A. A. Rafati A. R. A. Borujeni A. Hajian
Department of Physical Chemistry, Faculty of Chemistry, Bu-Ali Sina University, 65174 Hamedan,
Iran
1 3
J Solution Chem (2013) 42:20712086
DOI 10.1007/s10953-013-0093-8
the temperature of the system. This migration to the interface results in a liquid phase rich
in the component with the highest surface tension and a vapor phase rich in the component
with the lowest surface tension [24].
Models for calculation of surface tensions are normally based on the assumption that the
surface layer forms a separate phase with constant and uniform composition that is dif-
ferent from the composition of the adjacent vapor and bulk liquid phases. The models all
require values of the pure component surface tension for each component in the mixture.
The models differ in the way in which the molar surface areas of the components are
calculated and in the assumptions concerning the activity coefcients of the components,
both in the surface region and in the bulk liquid phases [5].
Several different approaches have been used to predict the surface tension and its
variation with composition: the classical thermodynamic method [69], corresponding
states models [10, 11], gradient theory [12], perturbation theory [13], the parachor method
[14], and also activity coefcient models such as Wilson, NRTL, and UNIFAC [5, 1517].
In this paper, we report experimental values of surface tension for binary mixtures of
diols {1,2-ethanediol (1,2-ED), 1,2-propanediol(1,2-PD), and 1,4-butanediol (1,4-BD)}
with acetonitrile, obtained using the ring method, and compare them with predicted surface
tensions from the Suarez method [5, 18, 19]. The model used here to estimate and predict
surface tension values for binary systems as a function of concentration and temperature
relates the surface concentration of each component to the individual activity coefcients
(in the liquid bulk phase and surface layer) and to the molar surface area of each com-
ponent [20]. The activity coefcients and the relative Gibbs adsorption were evaluated
using the UNIFAC group contribution model [2123].
The UNIFAC group contribution method is a g
E
(Gibbs energy) model that allows the
prediction of liquid phase activity coefcients c
i
in nonelectrolyte systems, as a function of
temperature and composition. The activity coefcient is calculated as the sum of the
combinatorial part and the residual part per pair of functional groups. The combinatorial
part represents the contribution of the excess entropy, which results from the different sizes
and shapes of the molecules considered. The residual part represents the contribution of the
excess enthalpy, which is caused by energetic interaction between the molecules [24, 25].
In addition to determining more information about the surface structure of binary
mixtures, surface mole fractions were calculated using the Suarez method (based on
UNIFAC model) and the extended Langmuir model (EL) [26]. The results obtained show a
good consistency between two applied methods, i.e., the Suarez method and EL model.
Finally, surface tension deviations were calculated from experimental data and have
been correlated with the RedlichKister (RK) and WangChen (WCH) polynomial
equations [9, 27].
2 Experimental
2.1 Materials
Acetonitrile (mass fraction [0.999), 1,2-ED (mass fraction [0.999), 1,2-PD (mass
fraction [0.99) and 1,4-BD (mass fraction [0.995), were purchased from Merck and
used without further purications. The water was distilled twice. Table 1 reports a com-
parison between the pure component density, q, and surface tension, r, at 298.15 K with
the corresponding literature values [2834].
The measured results are in good agreement with the literature values.
2072 J Solution Chem (2013) 42:20712086
1 3
2.2 Apparatus and Procedure
The surface tensions of the pure liquids and their mixtures were measured using the platinum
iridium ring method with a KSV (Sigma 70, Finland) tensiometer. Atechnical suggestion by
KSV is that the ring be amed prior to the measurements. The use of boiling distilled water
can be a good (alternative) procedure (for checking the performance of the KSV Sigma 70
system). However, the measurement of surface tension of water is very sensitive to dust or
grease which can occur on the ring. It often happens that the rst measurements of surface
tension fall well belowthe literature values (e.g. values of 64.68 mNm
-1
are obtained, which
is below the correct value of 71.97 mNm
-1
at 298.15 K). Following our experience, only
after cleaning the ring several times after soaking in chromosulfuric acid for several hours is it
possible to achieve stable measurements with water. When surface tensions are measured
with the ring detachment method, they are corrected to the actual values by means of the Huh
and Mason compensation for interface distortion [35].
Each measurement was repeated up to ten times to check for reproducibility. The
uncertainty of the surface tension measurement is 0.2 mNm
-1
of the nal value of
surface tension, and the corresponding reproducibility is 0.01 mNm
-1
. The temperature
was kept constant by a water bath circulator (Pharmacia Biotech) and with an uncertainty
of 0.1 K. The binary mixtures were prepared by mass using a Sartorius analytical bal-
ance (model BP 121S, accurate to 0.1 mg). The uncertainty of the mole fractions was
estimated to be within 1 9 10
-4
. Densities of pure components were measured with an
AntonPaar digital precision densitometer (Model DMA 4500) operated in static its mode
and calibrated with bidistilled water.
3 Results and Discussion
3.1 Prediction of Surface Tension for Binary Systems
Experimental values of the surface tensions for all binary mixtures at 298.15 K are listed in
Table 2. In all of the mixture systems, the surface tension, r, decreases with increasing
Table 1 Comparison of experimental surface tension, r, and density, q, of pure components with literature
values at 298.15 K and atmospheric pressure
Component r (mNm
-1
) q (gcm
-3
)
Exp. Lit. Exp. Lit.
Acetonitrile 28.10 28.25
a
, 28.16
b
0.77679 0.77664
c
1,2-ED 48.22 48.11
a
1.10978 1.0991
d
, 1.1086
e
1,2-PD 35.44 35.60
f
1.03211 1.0322
e
1,4-BD 45.33 45.47
f
1.01271 1.0126
g
a
Ref. [28]
b
Ref. [29]
c
Ref. [30]
d
Ref. [31]
e
Ref. [32]
f
Ref. [33]
g
Ref. [34]
J Solution Chem (2013) 42:20712086 2073
1 3
acetonitrile mole fraction. This trend is nonlinear and the surface tension decreases rapidly
with increasing acetonitrile concentration (see Fig. 1). This behavior is typically explained
as resulting from a difference in distribution of molecules between the surface and the bulk
of the liquid [17]. In a characteristic case, the compound having the lower surface tension
is expelled from the bulk to the liquidvapor interface due to the attractive forces between
solvent molecules (diols).
Relations for the surface tension of nonelectrolyte solutions can be derived based on the
assumption that the surface layer can be treated thermodynamically as a separate phase
from the bulk phase. The chemical potential of a component i in the bulk phase (b), l
i,b
, of
a nonelectrolyte solution is given by the relation:
l
i;b
l
0
i;b
RTlna
i;b
1
where l
0
i;b
is the standard chemical potential of component i in the bulk phase and a
i,b
is the
activity of component i in the bulk phase. R and T are the gas constant and absolute
temperature, respectively. In the surface phase (s), the chemical potential of a component
can be similarly written as
Table 2 Experimental and calculated values of the surface tension, r, of binary acetonitrile (2)/diol (1)
mixtures
x
2
r
exp
(mNm
-1
) r
cal
(mNm
-1
) x
2
r
exp
(mNm
-1
) r
cal
(mNm
-1
) APD (%)
Acetonitrile (2)/1,2-ED (1)
0.0109 47.82 47.63 0.2999 36.35 37.36 1.12
0.0199 47.46 47.16 0.3500 34.90 35.94
0.0361 46.85 46.36 0.4345 33.00 34.33
0.0720 45.45 44.75 0.4888 32.25 33.81
0.0845 44.97 44.23 0.5699 31.53 32.86
0.1012 44.23 43.58 0.6321 31.02 32.15
0.1402 42.70 42.17 0.7099 30.49 31.19
0.1862 40.78 40.71 0.7765 30.17 30.44
0.1992 40.13 40.33 0.8499 29.71 29.66
0.2569 37.76 38.79 0.9525 29.01 29.19
Acetonitrile (2)/1,2-PD (1)
0.0543 35.25 35.32 0.5217 32.25 31.37 1.78
0.0843 35.22 35.05 0.6503 31.43 30.43
0.0899 35.13 35.00 0.7504 30.83 29.75
0.2043 34.65 34.00 0.8106 30.50 29.67
0.2785 34.19 33.36 0.8895 29.66 29.57
0.4600 32.74 31.85 0.9493 28.69 28.51
Acetonitrile (2)/1,4-BD (1)
0.0086 45.30 45.21 0.4583 33.88 35.08 0.19
0.0341 45.13 44.47 0.4958 33.12 34.45
0.0544 44.88 43.90 0.6903 31.03 31.63
0.0997 44.10 42.68 0.7476 30.65 30.91
0.1963 41.70 40.29 0.8272 30.16 29.98
0.2813 38.81 38.42 0.8797 29.82 29.41
0.3504 36.59 37.03 0.9497 28.95 28.69
2074 J Solution Chem (2013) 42:20712086
1 3
l
i;s
l
0
i;s
RTlna
i;s
r

A
i
2
where r is the surface tension of the solution, a
i,s
the activity of component i in the surface
phase, and

A
i
the partial molar surface area of component i in the solution. For a pure
component with surface tension r
i
and molar surface area A
i
, it can be written as
l
0
i;s
l
0
i;b
rA
i
: 3
At equilibrium, the chemical potentials of component i in the bulk and surface phases
are equal, i.e.,
l
i;s
l
i;b
4
Combining Eqs. 14 leads to
r

A
i
rA
i
RTln
a
i;s
a
i;b
_ _
: 5
The activities a
i
in Eq. 5 can be written in terms of activity coefcients, c
i
, as
r

A
i
rA
i
RTln
x
i;s
c
i;s
x
i;b
c
i;b
_ _
6
where x
i,b
and x
i,s
are the mole fractions in the bulk and surface liquid phases, respectively,
and c
i,b
and c
i,s
are the corresponding activity coefcients.
Furthermore, the sum of the mole fractions over all components in the solution for both
bulk and surface liquid phases is unity:

i
x
i;b
1;

i
x
i;s
1 7
In the present work, we used two assumptions: (i) the bulk and surface phases are in
equilibrium; (ii) the partial molar surface area of component i is the same as the molar
surface area of i. Using these assumptions leads to the following equation [19, 25, 36, 37]:
28
31
34
37
40
43
46
49
0 0.2 0.4 0.6 0.8 1
x
2

/
(
m
N
.
m
-
1
)
Fig. 1 The experimental surface tension values, r, for the binary systems of acetonitrile (2)/diol (1) versus
x
2
: 1,2-ED (closed circle), 1,2-PD (closed square), 1,4-BD (closed triangle)
J Solution Chem (2013) 42:20712086 2075
1 3
r r
i

RT
A
i
ln
x
i;s
c
i;s
x
i;b
c
i;b
_ _
8
Application of Eqs. 7 and 8 requires knowledge of: (i) the surface tensions of the pure
components r
i
; (ii) the molar surface areas A
i
(the estimation of A
i
will be discussed in the
following section), and (iii) a model for calculating the activity coefcients c
i,s
and c
i,b
(in
this work the modied UNIFAC group-contribution method is used with the parameters
presented by Gmehling et al. [24]).
The surface tension predictions are found to be extremely sensitive to the values of the
molar surface areas used in the computation. There are two methods to calculate the molar
surface area: (i) Paquette molar surface areas, or (ii) Rasmussen molar surface areas [5, 38,
39]. In our previous work were evaluated the sensitivity of two methods (Rasmussen and
Paquette) in the prediction of surface tension [39]. In this paper, we used only the Paquette
method for calculation of molar surface areas. The equation for the Paquette molar surface
area is based on the assumption that the molecules are spherical and that the appropriate
geometrical area presented at the surface is the cross-sectional area of the molecule [38
40]:
A
i
1:021 10
8
V
6=15
i;c
V
4=15
i;b
9
Here V
i,c
is the critical molar volume and V
i,b
the bulk phase liquid molar volume of the
ith component, where V
i,c
and V
i,b
are in cm
3
mol
-1
and A
i
is in cm
2
mol
-1
.
For an N-component nonelectrolyte solution (i = 1 to N) with known composition (i.e.,
known x
i,b
), Eq. 8 forms a set of N equations in N unknowns (N - 1 independent mole
fractions x
i,s
and r). This set of equations is solved iteratively by the NewtonRaphson [23]
technique, and the values of c
i,s
and c
i,b
can be estimated by the UNIFAC group contri-
bution model [22, 39].
The surface tension values of the three binary organic systems predicted by this method,
and some derived parameters as well as experimental values, are tabulated in Table 2.
Also, the absolute percentage deviations (APD) have been calculated using the following
equation and the results are given in Table 2.
APD
100
N

i
r
i;exp
r
i;cal

r
i;exp
10
where N is the number of experimental data points.
The results obtained (Table 2) indicate that this method gives reliable predictions of the
surface tension. By considering the APD values, it has been shown that the proposed
method can be applied to estimate the surface tension for the binary mixtures of compo-
nents with the same chemical nature and molecular sizes.
There is a difference between r values obtained from the UNIFAC model and for the
experimental results (see Table 2). These discrepancies are due to the following: (i) exact
solutions of the equations were not possible, so an approximation method was used.
Therefore, the error will increase. It goes without saying that as the number of parameters
in the equation increases, the error will decrease. (ii) Due to the lack of values for molar
surface areas (A) for mixtures, we assume the same value of A for both pure materials and
their mixtures. On the other hand, the value of A has been considered to be the same for
bulk phase and surface. On the whole, by taking into account the above approximations,
our values obtained for APD are smaller than those reported by other researchers for
2076 J Solution Chem (2013) 42:20712086
1 3
similar systems, which suggests that the prediction method is reliable for determining the
surface tension of mixed solutions [5, 16].
3.2 Relative Gibbs Adsorption and Study of Surface Properties
The adsorption process involves the transport of molecules from the bulk solution to the
interface, where they form specially oriented molecular layers according to the nature of
the two phases. Adsorption of a component at the phase boundary of a system causes a
different concentration in the interfacial layer compared to the adjoining bulk phases. For
the adsorption of a component onto the uid interface, the relative Gibbs adsorption values,
C
2,1
, have been evaluated from the surface tension concentration data using the Gibbs
adsorption equation. Values of C
2,1
based on the arbitrary placement of the Gibbs dividing
plane near the uid interface is quantitatively related to the composition of the surface
phase. From the Gibbs equation, the relative adsorption was calculated according to the
expression:
C
2;1

or
ol
2
_ _
T;p

1
RT
or
olna
2
_ _
T;p
11
where l
2
and a
2
c
2
x
2
are the chemical potential and activity of component 2 in the
mixture, respectively. The values of c
2
were obtained using the UNIFAC model.
Figure 2 shows the variation of C
2,1
versus acetonitrile mole fraction (x
2
) in the bulk
solution. The positive value of C
2,1
in binary mixtures of the solvents indicates adsorption
of species No. 2 onto the surface (acetonitrile in our present study) and the addition of this
species to solutions causes the surface tension of the solution to decrease.
The C
2,1
value increases with increasing concentration of acetonitrile and nally reaches
maximum value of the saturated surface adsorption (C
max
2;1
). The values of C
max
2;1
(or C
2,1
) for
0
0.75
1.5
2.25
3
3.75
4.5
0.0 0.2 0.4 0.6 0.8
x
2

2
,
1

/
(

m
o
l
.

m
-
2
)
Fig. 2 The values of relative Gibbs adsorption, C
2,1
, against x
2
for the binary systems; the symbols were
calculated using the data and the continuous dashed curve is just a guide for the eyes: acetonitrile (2)/1,2-ED
(1) (closed circle), acetonitrile (2)/1,2-PD (1) (closed square), acetonitrile (2)/1,4-BD (1) (closed triangle)
J Solution Chem (2013) 42:20712086 2077
1 3
mixtures of diol (1,2-ED, 1,2-PD and 1,4-BD)/acetonitrile increase as follows: 1,2-
ED[1,4-BD[1,2-PD. On the other hand, the C
max
2;1
(or C
2,1
) decrease with increasing
differences between the surface tension values of the pure compounds.
In Fig. 2 there are two principal factors which induce the diol molecules to principally
avoid the interface: the lower surface tension of acetonitrile and the fact that the polar
interaction between diol molecules can be accomplished more efciently in the bulk liquid
phase instead of at the interface. Therefore, the acetonitrile molecules are expelled from
the bulk to the liquidvapor interface due to the attractive force among diol molecules (see
Fig. 3) [41, 42].
The surface layer concentration, x
2,s
, is the other quantity estimated simultaneously
using the calculation scheme proposed in this work (from Eq. 8 or the Suarez method).
Table 3 reports the x
2,s
values for the binary systems of diols (1,2-ED, 1,2-PD and 1,4-BD)
with acetonitrile at T = 298.15 K.
Also, the variation of x
2,s
versus x
2
for acetonitrile/diol mixtures is shown in Fig. 4 using
the above model. This diagram shows that the surface is enriched with solute (acetonitrile)
relative to the bulk composition. It is well recognized that, for processes that involve mass
transfer between liquid and vapor phases, surface tension plays an important role, and
according to what we have observed from the surface layer concentration curves, this
property is a consequence of the preferential migration of molecules of the different com-
ponents of a given mixture to the surface layer and eventually to the vapor phase [17, 25].
A new model (extended Langmuir, EL) was reported recently which describes the
surface tension of binary liquid mixtures as a function of the bulk composition [26, 43].
Briey, this model considers the surface of a binary liquid mixture as a thin but nite layer
and starts by developing the following expression for the relationship between the volume
fractions of component 2 in the surface and the bulk, u
s
2
and /
2
, respectively.
u
s
2

bu
2
1 b 1u
2
12
where the parameter b u
s
2
_
u
2

_
u
s
1
_
u
1
is a measure of the lyophobicity of compo-
nent 2 relative to component 1. In this model, the surface tension of non-ideal binary
mixtures is given by:
25
30
35
40
45
50
0.0 0.2 0.4 0.6 0.8 1.0
x
2

/
(
m
N
.
m
-
1
)
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5

2
,
1

/
(

m
o
l
.

m
-
2
)
Fig. 3 The experimental surface tension values, r, and adsorption isotherms, C
2,1
, against x
2
for acetonitrile
(2)/1,2-ED (1) mixtures at 25 C
2078 J Solution Chem (2013) 42:20712086
1 3
r u
s
1
r
1
u
s
2
r
2
ku
s
1
u
s
2
p
0
13
where r
1
and r
2
are the surface tensions of the pure components 1 and 2, respectively, p
0
is
the positive difference between them r
1
r
2
j j, and k is a parameter that represents the
effect of unlike-pair interactions on the surface tension of the mixture. Also, we continue to
regard component 1 as the component with higher surface tension. From Eq. 12, the
surface pressure, p = r
1
- r, can be written as:
p p
0
u
s
2
au
s
1
u
s
2
14
where a = k ? 1. By substituting for u
s
2
and (u
s
1
1 u
s
2
) from Eq. 12 into Eq. 14:
p
p
0
b b a/
1
=/
2

b /
1
=/
2

2
15
Table 3 The surface mole fraction of acetonitrile as a function of its bulk mole fraction, calculated on the
basis of the two models for the binary systems studied in this work
x
2
Suarez method EL x
2
Suarez method EL
x
2,s
x
2,s
x
2,s
x
2,s
Acetonitrile (2)/1,2-ED (1)
0.0109 0.0177 0.0165 0.2999 0.4224 0.3943
0.0199 0.0321 0.0299 0.3500 0.4810 0.4500
0.0361 0.0579 0.0538 0.4345 0.5730 0.5386
0.0720 0.1134 0.1055 0.4888 0.6277 0.5923
0.0845 0.1322 0.1230 0.5699 0.7034 0.6681
0.1012 0.1571 0.1461 0.6321 0.7568 0.7230
0.1402 0.2135 0.1986 0.7099 0.8182 0.7881
0.1862 0.2773 0.2580 0.7765 0.8662 0.8407
0.1992 0.2947 0.2743 0.8499 0.9147 0.8959
0.2569 0.3695 0.3444
Acetonitrile (2)/1,2-PD (1)
0.0543 0.0647 0.0481 0.5217 0.5702 0.4898
0.0843 0.0999 0.0749 0.6503 0.6939 0.6207
0.0899 0.1065 0.0800 0.7504 0.7860 0.7257
0.2043 0.2368 0.1843 0.8106 0.8396 0.7902
0.2785 0.3184 0.2536 0.8895 0.9257 0.9136
0.4600 0.5085 0.4285 0.9493 0.9583 0.9428
Acetonitrile (2)/1,4-BD (1)
0.0086 0.0131 0.0171 0.4583 0.5760 0.6285
0.0341 0.0513 0.0660 0.4958 0.6134 0.6629
0.0544 0.0811 0.1032 0.6903 0.7867 0.8168
0.0997 0.1458 0.1813 0.7476 0.8316 0.8556
0.1963 0.2756 0.3282 0.8272 0.8898 0.9054
0.2813 0.3810 0.4391 0.8797 0.9255 0.9360
0.3504 0.4609 0.5190 0.9497 0.9701 0.9742
J Solution Chem (2013) 42:20712086 2079
1 3
An iterative method has been used to derive the a and b parameters by inserting
experimental values in Eq. 15. Table 4 lists the values of the adjustable parameters a and b
obtained by tting Eq. 15 to the experimental results.
For some binary systems, values of a = 1 (k = 0) imply that the interactions do not
signicantly affect the surface tension of the solution and the deviation of surface tension
from ideal behavior is attributable exclusively to lyophobicity differences. The tting of
experimental results for some mixtures yields b[1, which indicates that the surface phase
is richer in the component with lower surface tension.
We calculated the surface volume fractions of solutes, u
s
2
, by using Eq. 12 and then
converted them to the surface mole fraction x
2,s
by the equation:
u
s
2

x
2;s
v
2
x
1;s
v
1
x
2;s
v
2
16
where x
2,s
is the number of moles of the 2nd component in the surface, and v
1
and v
2
are
molar volumes of components 1 and 2. The x
2,s
values obtained using the EL method are
comparable with those calculated via the Suarez method (see Table 3).
Also, the variation of x
2,s
- x
2
with x
2
is shown in Fig. 5. The x
2,s
- x
2
values are
positive in the whole composition range. This plot shows that the that the x
2,s
- x
2
values
increase with increasing difference of the surface tensions of the pure compounds (the
highest value of x
2,s
- x
2
is for an acetonitrile/1,2-ED mixture).
3.3 Correlation of Surface Tensions for Binary Systems
Finally, the deviations from ideal behavior can be quantied by surface tension deviations,
Dr, dened as:
Dr r

2
i1
x
i
r
i
17
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.2 0.4 0.6 0.8 1.0
x
2
x
2
,
s
Fig. 4 Calculated concentration of acetonitrile at the liquidvapor interface (x
2,s
) as a function of (x
2
) for
the binary systems of acetonitrile (2)/diol (1): 1,2-ED (closed circle), 1,2-PD (closed square), 1,4-BD (open
triangle)
2080 J Solution Chem (2013) 42:20712086
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where x
i
and r
i
are the mole fraction and surface tension of component i, respectively. For
the correlation of surface tensions of binary systems, an equation proposed by Redlich
Kister (RK) was used to describe the behavior of the observed systems [27]:
Dr x
i
x
j

pm
p0
A
p
x
i
x
j

p
18
where the A
p
are the adjustable parameters determined by a nonlinear least-squares opti-
mization method.
Wang and Chen (WCH) proposed an equation to correlate the surface tension data with
the composition of the binary systems [9, 44]:
r
x
i
B
ij
r
i
x
j
r
j
x
i
B
ij
x
j
D
ij
x
i
x
j
19
where r
i
and r
j
are the surface tensions of pure component i and j, respectively, and B
ij
and
D
ij
are the adjustable binary parameters.
In Table 5 the adjusted coefcients of the equations used to correlate the binary data are
listed as well as the respective standard deviations of the ts.
The standard deviation of the ts, S, is dened as:
S

M
i1
Dr
exp
Dr
cal

2
M P
_ _
1=2
20
Table 4 Values of the parame-
ters a and b, obtained by tting of
Eq. 15 with surface tension data
Systems a b
Acetonitrile (2)/1,2-ED (1) 1.78 1.52
Acetonitrile (2)/1,2-PD (1) 1.00 0.83
Acetonitrile (2)/1,4-BD (1) 1.31 2.01
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.0 0.2 0.4 0.6 0.8 1.0
x
2
x
2
,
s

-

x
2
Fig. 5 Values of x
2,s
- x
2
against x
2
for the binary systems: acetonitrile (2)/1,2-ED (1) (closed circle),
acetonitrile (2)/1,2-PD (1) (closed square), acetonitrile (2)/1,4-BD (1) (open triangle)
J Solution Chem (2013) 42:20712086 2081
1 3
where Dr
exp
and Dr
cal
are the experimental and calculated surface tensions deviations,
M the number of data points and P the number of adjustable parameters used for tting the
experimental data with various equations.
In Figs. 6 and 7 we have plotted the experimental and tted surface tensions of the
binary systems of acetonitrile/diol as a function of the composition with the RK and WCH
models. All of the binary mixtures show asymmetrical Dr behavior. As can be seen, the
agreement between the experimental data and correlated values are reasonable. All values
Table 5 Fitted coefcients and standard deviation, S, of the models used to correlate surface tension with
the composition for the binary systems at 298.15 K
Model A B C D E S (mNm
-1
)
Acetonitrile (2)/1,2-ED (1)
RK
a
-24.46 15.91 13.04 -15.01 0.07
WCH
b
2.23 -6.97 0.58
Acetonitrile (2)/1,2-PD (1)
RK
a
2.51 0.61 10.87 0.75 -9.63 0.06
WCH
b
10.03 0.68 0.15
Acetonitrile (2)/1,4-BD (1)
RK
a
-14.76 -1.57 30.02 -6.02 -7.29 0.06
WCH
b
10.18 -12.09 0.81
a
The coefcients A, B, C, D and E correspond to A
1
, A
2
, A
3
, A
4
and A
5
, respectively
b
The coefcients A and B correspond to B and D, respectively
Fig. 6 Surface tension deviation, Dr, as a function of the mole fractions of acetonitrile, for the binary
systems of acetonitrile (2)/diol (1). The symbols refer to the experimental data, and the dashed curves
represent the correlation with Eq. 18: 1,2-ED (closed circle), 1,2-PD (closed triangle), 1,4-BD (closed
square)
2082 J Solution Chem (2013) 42:20712086
1 3
of Dr, except those for the 1,2-PD/acetonitrile system, are negative over the whole
composition range.
Although the mixture of 1,4-BD with acetonitrile has slightly positive Dr values in the
region that is very rich in the 1,4-BD, it is suggested that the surface tension deviations
25
30
35
40
45
50
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
2

/
(
m
N
.
m
-
1
)
Fig. 7 Values of the surface tension, r, against the mole fraction of acetonitrile, for the binary systems of
acetonitrile (2)/diol (1). The symbols refer to the experimental data, and the dashed curves represent the
correlation with Eq. 19: 1,2-ED (closed circle), 1,2-PD (closed square)
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
-7
-6
-5
-4
-3
-2
-1
0
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x
2
-
x
2
,
s

/
(
m
N
.
m
-
1
)
x
2
Fig. 8 The surface tension deviations, Dr and x
2,s
- x
2
, versus x
2
for the binary systems of acetonitrile (2)/
diol (1): 1,2-ED (closed circle), 1,4-BD (closed triangle)
J Solution Chem (2013) 42:20712086 2083
1 3
indicate different distributions of unlike components between the surface and the bulk
region. The most negative values are reached in the mixture containing the pure com-
pounds showing the greatest difference in surface tension, that is 1,2-ED with acetonitrile.
The asymmetry in the curves of the 1,2-ED/acetonitrile and 1,2-PD/acetonitrile systems
indicates that the components with the strongest molecular interactions in each binary
mixture settle down in the bulk liquid phase instead of moving into the surface phase
between the liquid and vapor phases, shifting the curves to the rich region of these
compounds. Figure 8 is a typical plot showing the surface tension deviations (Dr) and
x
2,s
- x
2
as a function of composition for the acetonitrile/1,2-ED and acetonitrile/1,4-BD
systems. As observed in this gure, the variation of Dr and x
2,s
- x
2
with composition
distinctively follows the pattern. In these systems the Dr values are negative (rarely
positive) with a pronounced minimum and a specic maximum for x
2,s
- x
2
at the same
mole fraction of the component 2.
4 Conclusion
Surface tension values for binary mixtures of diols (1,2-ethanediol, 1,2-propanediol, and
1,4-butanediol) with acetonitrile are reported in this paper. The experimental results have
been compared with predictions by the Suarez method. The UNIFAC methods are used for
activity coefcients of the surface and bulk phases. Comparisons of the calculated surface
tensions with experimental data yield APD values, in the best case of less than 0.2 % for
the systems studied. Therefore, it is important to stress that this model can also give good
predictions for systems with a large polarity and asymmetrically range. We calculated
values of the surface mole fractions of solute using the EL model and compared them with
values obtained from the UNIFAC model. Finally, values of the experimental surface
tension were correlated by means of the RedlichKister and WCH equations that provide a
series of adjustable parameters for predicting surface tensions of such mixture systems.
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