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Fluid Phase Equilibria 429 (2016) 166e176

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Fluid Phase Equilibria


j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Group contribution method: Surface tension of linear and branched


alkanes
*, Lidmila Bartovska

Alena Randova
 5, 166 28 Prague 6, Czech Republic
University of Chemistry and Technology, Prague, Department of Physical Chemistry, Technicka

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 6 May 2016
Received in revised form
2 September 2016
Accepted 2 September 2016
Available online 4 September 2016

A group contribution method for predicting the surface tension of alkanes at various temperatures, based
on Guggenheim-Katayama-van der Waals equation, has been developed. The constants of this equation
evaluated from TRC Tables data for surface tension were used as a basis to determination contributions of
structural units. With knowledge of critical temperature of the liquid alkane it is possible to predict value
of its surface tension at various temperatures (from 273.15 to 333.15 K, or to temperature below the
normal boiling point). The data for 50 compounds were processed: 30 of them to determine contributions of structural units (main set), and remaining 20 compounds (denoted as test set) to verify the
proposed method. On the whole, 394 data points were used, 235 in the main set and 159 in the test set.
2016 Elsevier B.V. All rights reserved.

Keywords:
Surface tension
Alkanes
Group contribution method
Guggenheim-Katayama-van der Waals
equation

1. Introduction
The efcient design of the processes in chemical, petroleum,
pharmaceutical, or polymer industries can be performed if the
values of the thermophysical, physicochemical, and/or thermodynamic properties of the involved liquids are available. One of these
important physical properties is surface tension. Even though the
experimental data for surface tensions are plentiful nowadays, the
rapid development of industry needs large amounts of experimental data of surface tensions for a variety of substances at
different temperatures. Therefore, it is very useful to develop estimating methods with a wide range of applicability and good prediction accuracy. This work pays attention to the prediction of
surface tension of liquid alkanes by group contribution method.

1.1. Group contribution method (GCM)

1.2. Surface tension

Prediction/estimation of compound property is an important


question in the industry (it is signicant in simulation, modelling,
and controlling factories). Many laboratories are concentrated on
predicting properties of organic, inorganic, and biochemical compounds. One of the possibilities for prediction is a group
* Corresponding author.
E-mail addresses: randovaa@vscht.cz
(L. Bartovsk
a).

contribution method. Using group properties (assuming the


structure of the molecule is known) to predict total property of a
compound reduces the demand for experimental data considerably. The additive property may be calculated by summing up of the
contributions corresponding to certain parts of the molecules,
named units. A lot of GCM for a lot of properties has been already
compiled. The most popular are critical properties [1e6] and
enthalpy of vaporization [5,7e10]. Other examples are acentric
factor [11], density [12,13], activity coefcient [14,15], normal
boiling point [16], solvent activities in polymer solutions [17], gas
permeability in glassy polymer [18], probability and rate of aerobic
biodegradation [19], viscosity [20,21], Hansen solubility parameters
[22], toxicity of organic chemicals [23], octane number [24], second
virial coefcient [25], and least not last e surface tension, the
subject of this work.

(A.

http://dx.doi.org/10.1016/j.uid.2016.09.007
0378-3812/ 2016 Elsevier B.V. All rights reserved.

Randov
a),

bartovsl@vscht.cz

The boundary between a liquid phase and a gas phase can be


considered a third phase with properties distinct from those of the
liquid and gas e surface layer. The surface layer is in tension and
tends to contract to the smallest area compatible with the mass of
material, container restraints, and external forces, e.g., gravity. The
surface tension (g) is dened as the force exerted in the plane of the
surface per unit length. The thermodynamics of surface layers
presents an important and interesting part of science [26e32].

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova

1.3. Guggenheim-Katayama-van der Waals equation

Table 2
Characterization of compounds by structural units.

The principle of corresponding states may be safely regarded as


the most useful byproduct of van der Waals equation of state. This
principle can be applied to a variety of properties, such as e.g. the
critical state, the densities of coexistent phases, the vapour pressure
of the liquid, the entropy of evaporation, the heat capacity of the
liquid, and even to the temperature dependence of surface tension
of the liquids. The surface tension decreases with increasing temperature, in the critical point the vapour-liquid interface disappears
and the surface tension reaches zero.
Guggenheim [33] picked up the threads of van der Waals and
Katayama works and presented the Guggenheim-Katayama-van
der Waals equation:

g g0 $ 1 

T
Tc

n
(1)

where g0 and n are constants, T is temperature in K, and Tc is critical


temperature in K. Guggenheim's theoretically derived value of
n 11/9 holds true for ideal situation. In real systems the constant n
takes various values, from n 1.16 to n 1.5 [34]. In recent years,
equation (1) has been often used to correlation of surface tension
and the constants g0 and n were determined for many compounds
[35e38]. Equation (1) can be also used to estimation of critical
temperature [26,39e41] from experimental data on temperature
dependence of surface tension.
2. Developing of group contribution method
2.1. Denition of structural units
Various group contribution methods hitherto used either estimated directly the surface tension values [42,43], or the GCM were
applied to determination of parachor [44e49] from which the
surface tension was calculated.
The presented group contribution method is based on eq. (1),
similarly as in the work of Wu et al. [38] for ionic liquids. But
whereas they estimated only one of the constants, g0, and the
second constant, n, was assumed to have the Guggenheim's theoretical value of 11/9, our group contribution method is applied to
determination of both constants. The denition of structural units
and their description are presented in Table 1.
A detailed survey of all compounds together with their structural units is presented in Table 2. The principle of dening the
structural units is demonstrated on two examples shown in Fig. 1.
2.2. Dividing of compounds into groups
The compounds included into our study were divided into eight
groups: linear alkanes, alkylbutanes, alkylpentanes, alkylhexanes,
alkylheptanes, alkyloctanes, alkylcyclopentanes, and alkylcyclohexanes (Table 2; each compound was assigned its serial number
m).
Table 1
Structural units.
C-group units
CH3
CH2
CH
C
Geometry unit
b
c

Group
Group
Group
Group

167

CH3e (one single bond)


eCH2e (two single bonds)
> CHe (three single bonds)
> C< (four single bonds)

Number of C-bone units attached to the main skeleton or cycle


of molecule
Cycle in the molecule (cyclopentane or cyclohexane)

Compound

Linear alkanes
1
Hexane
2
Heptane
3
Octane
4
Nonane
5
decane
6
Undecane
7
Dodecane
8
Tridecane
Alkylbutanes
9
2-methylbutane
10
2,2-dimethylbutane
11
2,3-dimethylbutane
Alkylpentanes
12
2-methylpentane
13
2,2-dimethylpentane
14
2,3-dimethylpentane
15
2,2,3-trimethylpentane
16
2-methyl-3-ethylpentane
17
3-methyl-3-ethylpentane
18
2,2-dimethyl-3-ethylpentane
19
2,4-dimethyl-3-ethylpentane
20
3,3-diethylpentane
Alkylhexanes
21
2-methylhexane
22
2,2-dimethylhexane
23
2,3-dimethylhexane
24
3-ethylhexane
25
2,2,3-trimethylhexane
26
2-methyl-3-ethylhexane
27
3-methyl-3-ethylhexane
Alkylheptanes
28
2-methylheptane
29
2,2-dimethylheptane
30
2,3-dimethylheptane
Alkyloctanes
31
2-methyloctane
Alkylcyclopentanes
32
Methylcyclopentane
33
Ethylcyclopentane
34
Propylcyclopentane
35
Decylcyclopentane
36
1,1-dimethylcyclopentane
37
Isobutylcyclopentane
Alkylcyclohexanes
38
Methylcyclohexane
39
Ethylcyclohexane
40
Propylcyclohexane
41
Butylcyclohexane
42
Pentylcyclohexane
43
Hexylcyclohexane
44
Heptylcyclohexane
45
Octylcyclohexane
46
Nonylcyclohexane
47
Decylcyclohexane
48
1,1-dimethylcyclohexane
49
(1-methylpropyl)cyclohexane
50
(1,1-dimethylethyl)cyclohexane

CH3

CH2

2
2
2
2
2
2
2
2

4
5
6
7
8
9
10
11

3
4
4

1
1

3
4
4
5
4
4
5
5
4

2
2
1
1
2
3
2
1
4

3
4
4
3
5
4
4

3
3
2
4
2
3
4

3
4
4

4
4
3

1
2
2

1
1
1
1
2
2

4
5
6
13
4
5

1
1
1
1

1
2
3
10
2
4

1
1
1
1
1
1

1
1
1
1
1
1
1
1
1
1
2
2
3

5
6
7
8
9
10
11
12
13
14
5
6
5

1
1
1
1
1
1
1
1
1
1

1
2
3
4
5
6
7
8
9
10
2
4
4

1
1
1
1
1
1
1
1
1
1
1
1
1

CH

1
2
2

1
2
1
1
2
1
2
1
3

1
1
1
1

1
1
2
1
1
2

1
1

1
1

1
2

1
2
1

1
2
2
3
3
3
4
4
4
1
2
2
2
3
3
3

The above listed compounds were divided in two sets: one,


called the main set, comprising 30 members, from which the
contributional values of structural units were determined, and the
second, called the test set, comprising 20 members, serving to
validation of the proposed procedure. The classication of individual compounds, identied by their serial numbers, into the main
and test sets is shown in Table 3.

2.3. Errors
The contributions of the structural units were determined by

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova

168

the GCM constants were compared with TRC surface tension values
and with other data found in literature (Chapter 4).
3. Results of calculation
3.1. The contributions of structural units, the input data and data
predicted by GCM

Fig. 1. The examples of compounds and their structural units (left) 2,2-dimethyl-3ethylpentane: C-group units (5xCH3, 2xCH2, 1xCH, 1xC), , main skeleton, geometry
unit (B b 4 number of C-group units attached to the main skeleton of molecule)
(right) 1,1-dimethylcyclohexane: C-group units (2xCH3, 5xCH2, 1xC), geometry unit
(, c 1, B b 2 number of C-group units attached to the cycle).

minimization function S.

X

X j  X GCM;j

2

(2)

Table 4 displays the basic characteristics of the proposed group


contribution method.
The structural units and their contributional values are shown in
Table 5. The second column in this table (symbol a) represents the
number of liquids in the main set, in which this unit occurs. In the
test set each of aforesaid units can be found at least once.
The constants of eq. (1), g0 and n, were calculated by our GCM.
As can be seen from Table 6, these predicted values exhibit fair
agreement with the original data.
3.2. Errors

where j denotes the sequence number of the compound from the


main set, X represents g0 or n. The Microsoft EXCEL Solver was used
for the calculating.
The results obtained by the group contribution method were
compared with input data using the following statistical quantities:
a percentage error (Eq. (3)) and an average percentage error (Eq.
(4)).

 GCM;j

 Xj
X
$100
Xj

Dj X

(3)


P
Dj X

dX

(4)

2.4. Procedure
The input data, g0 and n, were obtained by processing the surface tension data from TRC Tables [50] according to Eq. (1) using the
average values of critical temperatures (the data on critical temperatures together with corresponding references are cited in the
Appendix e Table A1). These values of g0 and n were used to
evaluation of the contributions of structural units. Next step was to
calculate the g0 and n of each compound under study using these
contributions and to compare them with the input data (Chapter 3).
To demonstrate the applicability of the proposed approach, one
substance from each of the eight groups was taken and its surface
tension values calculated at various temperatures from Eq. (1) using

Table 3
Main and test sets.
Main set
1
5
6
8
9
10
12
13
16
19

Fig. 2 shows the values of percentage errors DX plotted against


m, the serial number of compound. The maximal percentage error
of g0 is 5.7% (isobutylcyclopentane, m 37, test set) and the
maximal percentage error of n is 4.1% (ethylcyclopentane, m 33,
main set). The average percentage errors in main set are 1.8% (g0)
and 1.5% (n), in test set are 2.2% (g0) and 1.7% (n). The overall percentage errors (all 50 compounds considered) were determined to
be 2.0% in g0 and 1.6% in n.
4. Evaluation of surface tension, comparison with
experimental values and discussion of results
4.1. Experimental methods for surface tension determination
Surface tension is measured as the energy required to increase
the surface area of a liquid by a unit of area. As surface tension
manifests itself by miscellaneous phenomena, there is a wide variety of methods for its measurement. The choice of the optimal
method depends on the nature of the liquid under investigation,
experimental conditions, as well as on the stability of the liquid
surface on deformation. Sometimes, however, the values of surface
tension obtained by different methods may not be the same.
Methods of measurement, cited in this work, are shortly introduced
in following part of text.
4.1.1. Capillary rise
Capillary rise method, based on the capillary elevation, is ranked
among the most accurate absolute method for determining the
surface tension of liquids. The rst mentions about capillarity are
very old [51e54], the theory of this method is described in detail.
This method is used up to this day [55e57]. Glass capillaries are
used most frequently, because the glass is transparent and is wetted
by most liquids.

Test set
20
21
23
24
25
27
28
29
31
32

33
35
36
38
40
41
44
46
47
49

2
3
4
7
11
14
15
17
18
22

26
30
34
37
39
42
43
45
48
50

Table 4
Statistics of the proposed GCM.
Number of compounds
Total points of surface tension
Number of compounds in main set
Points of surface tension in main set
Number of compounds in test set
Points of surface tension in test set
Number of structural unit

50
394
30
235
20
159
6

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova

169

Table 5
Contributions of structural units.
Structural unit
C-group unit
CH3
CH2
CH
C
Geometry unit
b
c

g0

30
30
20
7

24.40
0.56
22.89
47.71

0.562
0.017
0.527
1.079

17
11

0.56
54.67

0.005
1.138

4.1.2. Pendant drop method


The method is based on analysis of pendant drop prole [58,59].
The prole is scanned by a camera and geometry of a drop is
analyzed by computer program. This method is absolute, the
Fig. 2. Percentage errors in g0 and n.
Table 6
Predicted and original values of g0 and n.
m

Compound

Main set
1
Hexane
5
Decane
6
Undecane
8
Tridecane
9
2-methylbutane
10
2,2-dimethylbutane
12
2-methylpentane
13
2,2-dimethylpentane
16
2-methyl-3-ethylpentane
19
2,4-dimethyl-3-ethylpentane
20
3,3-diethylpentane
21
2-methylhexane
23
2,3-dimethylhexane
24
3-ethylhexane
25
2,2,3-trimethylhexane
27
3-methyl-3-ethylhexane
28
2-methylheptane
29
2,2-dimethylheptane
31
2-methyloctane
32
Methylcyclopentane
33
Ethylcyclopentane
35
Decylcyclopentane
36
1,1-dimethylcyclopentane
38
Methylcyclohexane
40
Propylcyclohexane
41
Butylcyclohexane
44
Heptylcyclohexane
46
Nonylcyclohexane
47
Decylcyclohexane
49
(1-methylpropyl)cyclohexane
Test set
2
Heptane
3
Octane
4
Nonane
7
Dodecane
11
2,3-dimethylbutane
14
2,3-dimethylpentane
15
2,2,3-trimethylpentane
17
3-methyl-3-ethylpentane
18
2,2-dimethyl-3-ethylpentane
22
2,2-dimethylhexane
26
2-methyl-3-ethylhexane
30
2,3-dimethylheptane
34
Propylcyclopentane
37
Isobutylcyclopentane
39
Ethylcyclohexane
42
Pentylcyclohexane
43
Hexylcyclohexane
45
Octylcyclohexane
48
1,1-dimethylcyclohexane
50
(1,1-dimethylethyl)cyclohexane

g0

g0(GCM)

n(GCM)

51.88
53.73
53.90
54.25
50.46
47.43
50.04
48.61
51.36
52.88
52.36
50.28
50.25
51.41
50.88
53.12
50.47
51.28
53.21
60.26
56.79
58.00
54.60
60.37
58.00
59.00
58.59
57.95
57.52
58.47

1.204
1.264
1.274
1.294
1.199
1.168
1.189
1.198
1.195
1.229
1.208
1.191
1.189
1.192
1.223
1.225
1.206
1.269
1.272
1.246
1.199
1.332
1.201
1.296
1.245
1.315
1.368
1.353
1.339
1.310

51.04
53.27
53.83
54.94
50.31
49.33
50.87
49.89
51.26
51.66
49.88
51.43
51.82
51.43
50.84
50.44
51.99
51.01
52.55
57.86
57.85
57.82
56.88
58.41
58.41
58.40
58.39
58.38
58.37
58.80

1.193
1.262
1.279
1.313
1.170
1.175
1.187
1.192
1.211
1.223
1.216
1.205
1.217
1.216
1.221
1.221
1.222
1.227
1.239
1.236
1.248
1.342
1.241
1.253
1.277
1.289
1.324
1.347
1.359
1.289

52.03
52.42
53.19
54.05
50.09
51.35
49.34
51.30
53.07
48.49
53.06
53.57
56.34
55.10
60.55
58.61
56.26
57.58
55.66
58.30

1.214
1.223
1.245
1.285
1.200
1.198
1.185
1.193
1.255
1.189
1.222
1.268
1.215
1.257
1.301
1.339
1.280
1.345
1.214
1.331

51.59
52.15
52.71
54.38
50.71
51.27
50.29
49.89
50.28
50.45
51.82
52.38
57.85
58.24
58.41
58.40
58.39
58.40
57.43
57.82

1.210
1.227
1.244
1.296
1.182
1.199
1.204
1.204
1.216
1.209
1.228
1.234
1.260
1.272
1.265
1.300
1.312
1.338
1.258
1.282

consumption of liquid is minimal, the measurement is possible at


high pressures and temperatures, or when the surface tension is too
low. The main problems of this method are lighting and vibrations.
Non-uniform lighting causes that the image of drop is asymmetric,
and owing to vibrations the image of drop may be unsharp.
4.1.3. Wilhelmy plate method
A universal method especially suited to check surface tension
over long time intervals. A glass or platinum vertical plate of known
perimeter is pulled through the interface and the force brought
about by wetting is measured [60]. The plate is usually roughened
to ensure complete wetting. In case of complete wetting no
correction factors are needed to calculate surface tension. The
method is suitable for systems with surfactants.
4.1.4. Du Noy ring method
The Du Noy ring method belongs to the most common force
balance methods. A small wire ring (Pt or Pt-Ir) lying in a plane
parallel to the liquid surface is at rst submerged in the liquid, then
slowly drawn up and the net uid force on the ring is monitored.
The ring with attached liquid meniscus is lifted above the undisturbed surface. The pull on the ring passes through a maximum;
further lifting of the ring causes only a reduction of pull. Supposing
the ring is perfectly wetted by the uid, the maximum pull on the
ring obtained during ring upheaval can be directly related to the
surface tension [60,61].
4.1.5. Maximum bubble pressure
The maximum bubble pressure technique is based on measuring
the pressure inside the bubbles continuously generated at the tip of
the capillary immersed in the liquid under study. The gas pressure
is recorded during the bubble formation and detachment. It reaches
maximum when the bubble radius is the same as capillary radius.
Beyond that, the bubble becomes unstable and detaches itself from
the capillary. The surface tension is then calculated from this
maximum pressure and the capillary radius. The maximum bubble
pressure method was introduced more than 160 years ago [62].
Bubble pressure tensiometry is widely utilized to study various
dynamic surface phenomena including industrial and biological
applications.
4.1.6. Drop-weight method
The method is based on determination of the average mass of a
droplet detaching from the grounded tip of a thick-walled capillary.
The drop detaches as soon as its weight surpasses the surface forces

170

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova

acting along the outer perimeter of capillary tip. The resulting


droplet weight is either corrected by a factor taking into account
the small droplets arising at the same time with the large main
droplet, or the measurement is performed using a reference liquid
with the similar properties as the measured liquid [63,64].
4.2. Calculated and literature values of surface tension
The quality of the parameters of eq. (1) estimated by our GCM
method has been tested on several sample cases. The surface tensions of eight casually selected compounds (one from each group)
calculated for various temperatures were compared with TRC data
and with further data found in literature. The comparison is presented in Figs. 3e6. It can be seen that values obtained by the
method proposed in this work are in reasonable agreement with
experimental data. The properties of these compounds are gathered in Table A2 in Appendix.
Heptane is a member of linear alkanes group. It is a totally nonpolar solvent with low density (r 0.68 g cm3 at 25  C) and
boiling point 371.58 K [37]. It is a compound with well-known
properties, therefore a large amount of data on the surface tension has been found in literature. Although the methods of measurement are different (capillary rise method [65,66], pendant drop
method [59], Wilhelmy plate/Du Nouy ring [60]), the obtained
surface tension values at the same temperatures are practically the
same. It can be seen that the proposed GCM method (Fig. 3, full line)
predicted the surface tension of this compound very well. 2methyl-3-ethylhexane is more complex molecule (two branching
group), with higher density (r 0.73 g cm3 at 25  C), and slightly
higher boiling point (411.15 K [69]). The values of surface tension
predicted by the presented GCM are in a reasonable agreement
with TRC Tables data [50], used as a basis for our GCM (Fig. 3). The
other literature data [28,68,71] of surface tension are in a good
agreement with TRC Tables data [50]. These two liquids are
different in many respects, but their viscosities (h (heptane) 0.40 mPa s and h (2-methyl-3-ethylhexane) 0.43 mPa s,
both at 25  C) and solubility parameters (d (heptane) 15.21 MPa1/
2
and (d (2-methyl-3-ethylhexane) 15.25 MPa1/2) are very near.
Fig. 4 displays the surface tension data for 2,2-dimethylbutane
and 1,1-dimethylcyclohexane e two substances with quaternary
carbon and the same acentric factor (u 0.23). Their other properties like solubility parameters, van der Waals volumes, viscosities,
or boiling points, are however not very similar. 2,2-

Fig. 3. Calculated and literature surface tension of heptane and 2-methyl-3ethylhexane as a function of temperature.

Fig. 4. Calculated and literature surface tension of 2,2-dimethylbutane and 1,1dimethylcyclohexane as a function of temperature.

Dimethylbutane belongs to the group of alkylbutanes. Its density


is low (r 0.64 g cm3 at 25  C). Only one set of experimental data
on surface tension at various temperatures, obtained by capillary
rise method, was found in literature [66], the other data shown in
Fig. 4 were found either in data compilations [28,66] (no details
mentioned) or they were obtained by theoretical calculation (correlation between topological features and surface tension) [67]. The
boiling point of 2,2-dimethylbutane is 322.85 K [69], consequently
the surface tension data in TRC Tables [50] and those in this work
range only to 313.15 K. However, the data, presented in Ref. [66],
extend well above the boiling point, so there is no wonder that
some discrepancies can be observed (Fig. 4). 1,1-dimethylcyclohexane, one of alkylcyclohexanes, has the highest density from those eight chosen sample compounds (r 0.78 g cm3 at
25  C). The predicted surface tension data are in a very good
agreement with all available literature data [28,50,68,71].
The surface tension e temperature plots in Fig. 5 belong to two
compounds with linear main chain, which differ only by two CH2groups. 2-Methylpentane also counts among the low-density liquids (r 0.65 g cm3 at 25  C). The literature data comprise both e

Fig. 5. Calculated and literature surface tension of 2-methylpentane and 2methylheptane as a function of temperature.

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova

171

critical temperature (Tc 599.6 K) from the eight selected compounds. But other physico-chemical properties (acentric factor,
boiling point, van der Waals volume) are not of extreme values. The
literature data (capillary rise method [28], data compilations
[68,71]) are in very good agreement with our data (see Fig. 6), just
like in case of 2-methyloctane [28,68,71]. This substance boiling
point is the highest from our eight selected compounds (416.43 K
[37]), and so is also the acentric factor.
4.3. Calculation methods for surface tension determination
4.3.1. Parachor
The parachor belongs to the most known quantities which are
denoted as additive. At temperatures sufciently distant from the
critical state, where the vapour density can be neglected, the parachor is almost independent of temperature and can be calculated
from individual atomic and structural contributions [73]. Knowing
the molar mass of liquid M and its density r, this value of parachor
can be used to estimate the surface tension:
Fig. 6. Calculated and literature surface tension of 2-methyloctane and propylcyclopentane as a function of temperature.

g
calculation [67] and experimental (maximum bubble pressure
method) [70]. Viscosity of this substance (h 0.28 mPa s at 25  C) is
the smallest of all eight compounds under consideration. Also its
acentric factor (0.28) and van der Waals volume (68.3 cm3 mol1)
are very low. The main chain of 2-methylheptane consists of an
odd number of carbon atoms (7) like 2-methylpentane (5). The
properties of 2-methylheptane are approximately by 25% higher
than those of 2-methylpentane, and so are their surface tensions.
Fig. 5 points out to very good agreement between the surface
tension values calculated by GCM and literature data (in case of 2methylpentane: [28] and [68] e data compilations, [67] e correlation method, [70] e capillary rise and bubble pressure methods,
and in case of 2-methylheptane: [28] and [68] e data compilations,
[72] e maximum bubble pressure, [58] e measurement by pendant
drop method).
Propylcyclopentane has the highest solubility parameter (16.4),
the highest viscosity (h 0.65 mPa s at 25  C), and also the highest

r$P

4
(5)

4.3.2. Quantitative structureproperty relationship (QSPR) model


This model [74] uses the relative topological distance to show
the effect of the linking mode of each functional group, which can
reect the contribution of the same functional group for the surface
tension. The authors used regression model with two descriptors to
predict the surface tension. These descriptors are calculated from
molecular structure, the input data are based on the Pauling electronegativity. This model comprises a number of organic substances (92), but does not include the temperature dependence e
all surface tension data are at 20  C.
4.3.3. Romero-Martnez estimation method
Romero-Martnez et al. [75,76] proposed a method for estimation and prediction of pure hydrocarbons and their isomers. The
fact that the value of surface tension for an isomer was found to be

Table 7
Comparison of calculation methods with method presented in this work, the values of surface tension are in mN m1, the values of percentage difference are in %.
T/K

[50]

Heptane
293.15
20.14
298.15
19.65
2-methyl-3-ethylhexane
293.15
22.80
298.15
22.34
2,2-dimethylbutane
293.15
16.30
298.15
15.81
1,1-dimethylcyclohexane
293.15
24.12
298.15
23.61
2-methylpentane
293.15
17.38
298.15
16.87
2-methylheptane
293.15
20.60
298.15
20.14
2-methyloctane
293.15
21.88
298.15
21.41
Propylcyclopentane
293.15
24.95
298.15
24.46

This work

4.3.1

4.3.2

4.3.3

dthis work

d4.3.1

d4.3.2

d4.3.3

20.03
19.54

19.25
18.78

19.79

19.99
19.47

0.55
0.56

4.40
4.45

1.74

0.74
0.90

22.20
21.74

23.42
22.91

22.7

22.53
22.05

2.63
2.69

2.73
2.57

0.44

1.20
1.30

16.83
16.33

16.61
16.14

17.02

16.50
16.00

3.27
3.28

1.91
2.06

4.42

1.21
1.23

24.25
23.75

23.94
23.43

0.53
0.56

0.76
0.76

17.70
17.18

17.03
16.55

17.45

17.35
16.83

1.81
1.85

2.04
1.91

0.40

0.18
0.23

21.00
20.52

19.96
19.50

20.87

20.68
20.20

1.93
1.87

3.10
3.17

1.31

0.39
0.30

22.15
21.68

21.01
20.57

22.17

22.13
21.66

1.22
1.24

3.95
3.92

1.33

1.15
1.18

24.83
24.33

24.10
23.60

0.46
0.55

3.41
3.53

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova

172

very close to value of the corresponding normal hydrocarbon at the


same temperature was used to compile a method allowing to estimate the surface tension of isomers as a function of temperature.
Relatively large amounts of input data are needed: molar volume of
n-alkane and isomer, total solubility parameter of n-alkane and
isomer e to calculation of adjustable parameter; molar mass, critical temperature, and two other adjustable parameters e to
calculation of surface tension of n-alkane. This method gives more
accurate results than the previous two, but requires knowledge of
properties of both, the isomer and corresponding n-alkane.
4.4. Comparison of surface tension values obtained by various
calculation methods

gcalc  g50
$100%
g50

Acknowledgement
Authors thank to UCT (University of Chemistry and Technology)
Prague Institutional support e specic university research 2016.
Appendix
Appendix A. Input data

The three above-mentioned calculation methods (4.3.1, 4.3.2,


and 4.3.3) were compared with the method proposed in this work.
The resulting values of surface tension are presented in Table 7,
together with the percentage difference (di) between values obtained by calculations and data used as the input data in this work
[50] is expressed as

di

no matter what was the structure of the compound (linear alkanes,


branched alkanes, branched cycloalkanes) and no matter whether
the compound was placed into the main or the test set.

Table A1
Critical temperatures of liquids together with their references.

Hexane
C6H14
M 86.175 g mol

(6)

where gcalc is surface tension obtained by the appropriate method


and g [50] is surface tension found in TRC Tables. The comparison
was made for the same eight compounds that were selected for
testing GCM presented in this work (see 4.2). The single calculations are marked by numbers of previous section (4.3.1, 4.3.2, and
4.3.3).
Since two of the three considered methods do not allow the
calculation for the cyclic hydrocarbons (methods described in 4.3.2
and 4.3.3), some cells in Table 7 are unlled. The calculations based
on parachor (4.3.1) include all eight compounds, but this method is
least accurate. As mentioned above, the most important disadvantage of method described in 4.3.2 is that the calculations are
possible only for one temperature. Even though the last method
(4.3.3) gives the smallest values of percentage differences, it is more
laborious and requires more input data. Moreover if the properties
of unbranched substance is not known, the calculation of the isomer surface tension is not possible.

Average critical temperature


Tc 507.6 K
Heptane
C7H16
M 100.202 g mol

1

Average critical temperature


Tc 540.3 K
Octane
C8H18
M 114.229 g mol

1

Average critical temperature


Tc 568.8 K
4

Nonane
C9H20
M 128.255 g mol

5. Conclusions
A group-contribution method for predicting the constants of
Guggenheim-Katayama-van der Waals equation describing the
temperature dependence of surface tension for alkanes has been
developed. The method is based on these constants values evaluated from the surface tensions of 30 alkanes, taken from TRC Tables.
The structural units were dened (units of C-group and units of
geometry) and their contributions were determined from the data
for 30 alkanes.
The proposed GCM method was veried on g0 and n data for
further 20 alkanes (test set). The average percentage errors in main
set are 1.8% (g0) and 1.5% (n), in test set are 2.2% (g0) and 1.7% (n).
The overall percentage errors (all 50 compounds considered) were
determined to be 2.0% in g0 and 1.6% in n. These values show that
our group contribution method is able to predict the constants of
the chosen equation.
To demonstrate the applicability of the method for the surface
tension determination, the comparison of the data for eight casually chosen compounds calculated by GCM method as a function of
temperature with those found in literature is shown. This comparison revealed that the surface tension values acquired by GCM
calculation were in good agreement with available literature data

1

1

Average critical temperature


Tc 594.8 K
Decane
C10H22
M 142.282 g mol

1

Average critical temperature


Tc 617.8 K

Undecane
C11H24
M 156.308 g mol1
Average critical temperature
Tc 638.9 K

Dodecane
C12H26
M 170.335 g mol1

Average critical temperature


Tc 658.1 K
Tridecane
C13H28
M 184.361 g mol1

Tc/K

Ref

507.5
507.6
507.5
507.4
507.8
507.6

[50]
[77]
[78]
[79]
[80]
[37]

540.3
540.2
540.3
540.3
540.2
540.6

[50]
[77]
[78]
[79]
[37]
[81]

568.83
568.7
568.83
568.8
568.7
568.88
568.82

[50]
[77]
[78]
[79]
[37]
[82]
[65]

594.6
594.6
594.6
595.7
594.6
594.55

[50]
[77]
[78]
[79]
[37]
[82]

617.9
617.7
617.7
618.5
617.7
617.7
617.5
617.54

[50]
[77]
[78]
[79]
[37]
[82]
[83]
[84]

639
639
638.8
639
638.8
639

[50]
[77]
[78]
[37]
[82]
[85]

658.2
658
658.2
658
658.1
658.2

[50]
[77]
[78]
[37]
[82]
[85]

675.8
675
676
675

[50]
[77]
[78]
[37]

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova
Table A1 (continued )

10

14

15

16

17

18

19

20

21

1

Average critical temperature


Tc 500 K
2-methylpentane
C6H14
M 86.175 g mol

13

1

Average critical temperature


Tc 488.9 K
2,3-dimethylbutane
C6H14
M 86.175 g mol

12

1

Average critical temperature


Tc 460.5 K
2,2-dimethylbutane
C6H14
M 86.175 g mol

11

Table A1 (continued )

Average critical temperature


Tc 675.6 K
2-methylbutane
C5H12
M 72.149 g mol

173

1

Average critical temperature


Tc 497.7 K
2,2-dimethylpentane
C7H16
M 100.202 g mol1
Average critical temperature
Tc 520.5 K
2,3-dimethylpentane
C7H16
M 100.202 g mol1
Average critical temperature
Tc 537.3 K
2,2,3-trimethylpentane
C8H18
M 114.229 g mol1
Average critical temperature
Tc 563.5 K
2-methyl-3-ethylpentane
C8H18
M 114.229 g mol1
Average critical temperature
Tc 567 K
3-methyl-3-ethylpentane
C8H18
M 114.229 g mol1
Average critical temperature
Tc 576.5 K
2,2-dimethyl-3-ethylpentane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 590.5 K
2,4-dimethyl-3-ethylpentane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 592.2 K
3,3-diethylpentane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 610.1 K
2-methylhexane

Tc/K

Ref

675.9
675.8

[82]
[85]

C7H16
M 100.202 g mol1

460.39
460.4
460.4
460.95
460.51
460.4

[50]
[78]
[37]
[86]
[87]
[79]

488.7
489
488.78
489.25
489
488.8

[50]
[37]
[78]
[88]
[89]
[79]

Average critical temperature


Tc 530.3 K
2,2-dimethylhexane
C8H18
M 114.229 g mol1
Average critical temperature
Tc 549.8 K
2,3-dimethylhexane
C8H18
M 114.229 g mol1

499.9
500
499.98
500.23
500
500

[50]
[37]
[78]
[88]
[89]
[79]

497.5
497.7
497.5
497.5
498.05
497.7

[50]
[37]
[78]
[79]
[88]
[89]

520.4
520.5
520.5
520.5

[50]
[37]
[78]
[89]

27

537.3
537.3
537.35
537.4
537.3

[50]
[37]
[78]
[79]
[89]

28

563.4
563.5
563.5
563.5
563.5

[50]
[37]
[78]
[79]
[89]

567
567
567.09
567.1
567

[50]
[37]
[78]
[89]
[79]

576.5
576.5
576.58
576.5

[50]
[37]
[78]
[89]

589.5
590
592.1
590.4

[50]
[37]
[71]
[68]

588.5
591
591.25
598

[50]
[37]
[71]
[68]

610.2
610.05
610.1
610
610

[50]
[37]
[79]
[71]
[68]

22

23

24

25

26

29

30

31

32

33

34

35

Average critical temperature


Tc 563.5 K
3-ethylhexane
C8H18
M 114.229 g mol1
Average critical temperature
Tc 565.5 K
2,2,3-trimethylhexane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 588.1 K
2-methyl-3-ethylhexane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 588.2 K
3-methyl-3-ethylhexane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 597.8 K
2-methylheptane
C8H18
M 114.229 g mol1
Average critical temperature
Tc 559.6 K
2,2-dimethylheptane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 577.0 K
2,3-dimethylheptane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 589.7 K
2-methyloctane
C9H20
M 128.255 g mol1
Average critical temperature
Tc 583.9 K
Methylcyclopentane
C6H12
M 84.16 g mol1
Average critical temperature
Tc 532.8 K
Ethylcyclopentane
C7H14
M 98.186 g mol1
Average critical temperature
Tc 569.5 K
Propylcyclopentane
C8H16
M 112.213 g mol1
Average critical temperature
Tc 599.6 K
Decylcyclopentane

Tc/K

Ref

530.1
530.4
530.4
530.4
530.37

[50]
[37]
[89]
[79]
[78]

549.8
549.8
549.87
549.8

[50]
[37]
[78]
[89]

563.4
563.5
563.49
563.5
563.4

[50]
[37]
[78]
[89]
[79]

565.4
565.5
565.5
565.49

[50]
[37]
[89]
[78]

587
588
588.05
589.4

[50]
[37]
[68]
[71]

587.4
588.1
588.1
589.2

[50]
[37]
[68]
[71]

597.6
597.5
597.55
598.4

[50]
[37]
[68]
[71]

559.6
559.64
559.64
559.7

[50]
[78]
[37]
[89]

577.8
576.8
576.7
576.7

[50]
[78]
[37]
[89]

588.8
589.6
589.6
590.6

[50]
[37]
[68]
[71]

587
582.9
582.8
582.8

[50]
[78]
[37]
[89]

532.79
532.73
532.8
532.79
532.7

[50]
[78]
[79]
[37]
[89]

569.5
569.5
569.5
569.5
569.5

[50]
[78]
[79]
[37]
[89]

596.2
596
603.15
603

[50]
[37]
[68]
[71]

(continued on next page)

, L. Bartovska
 / Fluid Phase Equilibria 429 (2016) 166e176
A. Randova

174
Table A1 (continued )

36

37

38

39

40

41

42

43

44

45

46

47

48

49

C15H30
M 210.399 g mol1
Average critical temperature
Tc 731.3 K
1,1-dimethylcyclopentane
C7H14
M 98.186 g mol1
Average critical temperature
Tc 547.7 K
Isobutylcyclopentane
C9H18
M 126.239 g mol1
Average critical temperature
Tc 622.8 K
Methylcyclohexane
C7H14
M 98.186 g mol1
Average critical temperature
Tc 572.2 K
Ethylcyclohexane
C8H16
M 112.213 g mol1
Average critical temperature
Tc 606.9 K
Propylcyclohexane
C9H18
M 126.239 g mol1
Average critical temperature
Tc 629.9 K
Butylcyclohexane
C10H20
M 140.266 g mol1
Average critical temperature
Tc 654.6 K
Pentylcyclohexane
C11H22
M 154.292 g mol1
Average critical temperature
Tc 677.8 K
Hexylcyclohexane
C12H24
M 168.319 g mol1
Average critical temperature
Tc 695.9 K
Heptylcyclohexane
C13H26
M 182.346 g mol1
Average critical temperature
Tc 712.3 K
Octylcyclohexane
C14H28
M 196.372 g mol1
Average critical temperature
Tc 728.5 K
Nonylcyclohexane
C15H30
M 210.399 g mol1
Average critical temperature
Tc 740.8 K
Decylcyclohexane
C16H32
M 224.425 g mol1
Average critical temperature
Tc 754.3 K
1,1-dimethylcyclohexane
C8H16
M 112.213 g mol1
Average critical temperature
Tc 589.8 K
(1-methylpropyl)cyclohexane
C10H20
M 140.266 g mol1
Average critical temperature
Tc 668.4 K

Table A1 (continued )
Tc/K

Ref

729.1
730.64
742.4
723.15

[50]
[37]
[71]
[92]

547
547
547
547
550

[50]
[78]
[37]
[68]
[71]

617.21
625.65
625.6

[37]
[68]
[71]

572.19
572.2
572.2
572.1

[50]
[78]
[79]
[37]

602.4
609.2
609.15
606.9

[50]
[79]
[37]
[90]

625.6
639.15
630.8
624

[50]
[37]
[90]
[91]

648.4
667
653.1
650

[50]
[37]
[90]
[91]

669
674.01
684
684

[50]
[37]
[68]
[71]

687.7
691.81
702
702

[50]
[37]
[68]
[71]

704.7
708.63
718
718

[50]
[37]
[68]
[71]

720.3
723.61
735
735

[50]
[37]
[68]
[71]

750
734.6
737.79

[71]
[50]
[37]

2-Methyl-3-ethylpentane

Heptane

Main set
4xCH32xCH22xCH3xb

Test set
2xCH35xCH2

764
747.7
751.25

[71]
[50]
[37]

g0

585.8
591.15
591.15
591

[50]
[37]
[68]
[71]

667
669
669.15

[37]
[68]
[71]

50

(1,1-dimethylethyl)cyclohexane
C10H20
M 140.266 g mol1
Average critical temperature
Tc 659.2 K

Tc/K

Ref

667
652
659
659.15
659

[37]
[90]
[93]
[68]
[71]

Table A2
Properties of eight sample compounds [37,94,95].
Tb/K

Tc/K

Heptane
371.58 540.3 0.35
2-methyl-3-ethylhexane
411.16 588.2 0.378
2,2-dimethylbutane
322.88 488.9 0.234
1,1-dimethylcyclohexane
392.7
589.8 0.233
2-methylpentane
333.41 497.6 0.279
2-methylheptane
390.8
559.6 0.377
Propylcyclopentane
404.11 599.6 0.327
2-methyloctane
416.43 583.9 0.458

r/g cm3

Hvap/
kJ mol1

h/mPa s

d/

(25  C)

(25  C)

MPa1/2

Vvdw/cm3
mol1

0.68

31.731

0.395

15.213

78.49

0.73

35.982

0.433

15.253

98.93

0.64

26.416

0.337

13.766

68.24

0.78

32.443

0.527

15.677

81.82

0.65

24.942

0.278

14.414

68.25

0.7

33.436

0.463

15.373

88.71

0.77

34.593

0.653

16.394

80.62

0.71

36.426

0.426

15.326

98.94

Appendix B. Example of calculation


Into this section were chosen two liquids: 2-methyl-3ethylpentane (from main set) and heptane (from test set). Surface
tension values were found in literature and g0 and n were calculated (see Table B1). The structure of liquid molecules were divided
into structural units (the list of structural units and their description is presented in Table 1). The liquids from main set were used as
a basis for calculation of contributions of single structural units.
These contributions were used to calculation of g0(GCM) and
n(GCM) of liquids in main set and test set. The calculated surface
tensions were determined using these values g0(GCM) and n(GCM)
and are compared with the literature (Table B1). The calculated
values are in good agreement with literature.

Table B1
Calculations.

GCM
51.263
1.211

51.357
1.195

T/K

g (mN m1)
Literature

Calculated

273.15
283.15
293.15
298.15
303.15
313.15
323.15
333.15

23.4
22.5
21.5
21.1
20.6
19.7
18.7
17.8

23.1
22.2
21.2
20.8
20.3
19.4
18.4
17.5

g0

GCM
51.594
1.210

52.026
1.214

T/K

g (mN m1)
Literature

Calculated

273.15
283.15
293.15
298.15
303.15
313.15
323.15
333.15

22.1
21.1
20.1
19.7
19.2
18.2
17.2
16.2

22.0
21.0
20.0
19.5
19.1
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