Journal of Molecular Liquids 224 (2016) 125131

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Isobaric (vapor + liquid) equilibria for 2-methylthiophene with

n-heptane, 2,2,4-trimethylpentane, n-nonane and n-decane at 90.00 kPa
Junzhi Li, Junqiang Wang, Wei Zhao, Xiaoliang Li
State Key Laboratory Breeding Base of Coal Science and Technology Co-founded by Shanxi Province, Ministry of Science and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi,
PR China

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

Article history: Isobaric vapor-liquid equilibrium (VLE) data for the four systems n-heptane + 2-methylthiophene, 2,2,4-
Received 12 June 2016 trimethylpentane + 2-methylthiophene, n-nonane + 2-methylthiophene, n-decane + 2-methylthiophene
Received in revised form 20 September 2016 were measured at 90.00 kPa with a modied Rose-Williams still. Gas chromatography equipped with a ame ion-
Accepted 28 September 2016
ization detector was used to analyze composition of the samples from the vapor-liquid equilibrium systems. All
Available online 30 September 2016
the VLE measurements passed the thermodynamic consistent test using the Herington method and the Van Ness
Keywords:
test. The azeotropic behavior was found in the 2,2,4-trimethylpentane + 2-methylthiophene system. The exper-
Vapor-liquid equilibrium imental data were correlated by the Wilson and NRTL activity coefcient models and also compared with the
2-Methylthiophene original UNIFAC predictive model. The corresponding parameters for the three models were obtained. The results
Wilson model exhibited that the measured data got agree well with the calculated values using the Wilson, NRTL and original
NRTL model UNIFAC models.
Original UNIFAC model 2016 Elsevier B.V. All rights reserved.

1. Introduction methylthiophene and 2,4,4-trimethyl-1-pentene + 2-methylthiophene

The emission of sulfur oxides (SOx) formed by the combustion of sul-
fur compounds in transportation fuels has received tremendous atten-
tion as they can result in the deactivation of auto-exhaust catalyst and
air pollution. Thus, the regulations to restrict the sulfur content in
fuels are increasingly stringent in many countries. The regulation in
the Canada and the USA, which was regulated in 2006, reduced the sul-
fur content in diesel and gasoline from 500 ppm by weight (ppmw) and
350 ppmw to 15 ppmw and 30 ppmw, respectively [1]. In China, the
upper limit of 150 ppmw for sulfur content in gasline has been carried
out since 2010 [2]. Zero-emission and zero-levels of sulfur content are
previewed for the coming 510 years [3].
Most of the fuels, which come from uid catalytic cracking unit, gen-
erally contain hydrocarbons and organic sulfur compounds. In order to
meet the increasingly strict requirements for sulfur content in fuels, opti-
mal design of the desulfurization process plays an important role. In the
design and operation of fuel desulfurization processes, the information
of VLE data for the sulfur compound is required [4]. In the case of 2-
methylthiophene, which is one of the representative thiophenic
organosulfur compounds in the fuel, very few literatures have reported
its VLE data until now. Giles et al. have reported the VLE data for 1-octane
+2-methylthiophene at 373.15 K and 413.15 K [5]; Sapei et al. have stud-
ied the VLE data for binary systems of 2,2,4-trimethylpentane + 2-
Corresponding author.
E-mail address: lixiaoliang@tyut.edu.cn (X. Li).
at 358.15 K and 368.15 K [6]. However, the above VLE data of 2-
methylthiophene were measured under isothermal conditions. For the
purpose of designing the separation processes accurately, more experi-
mental VLE data for 2-methylthiophene + hydrocarbons binary system
is still urgent needed.
In this work, isobaric VLE data for n-heptane + 2-
methylthiophene, 2,2,4-trimethylpentane + 2-methylthiophene, n-
nonane + 2-methylthiophene, n-decane + 2-methylthiophene sys-
tems was measured at 90.00 kPa with a modied Rose-Williams
still and was reported for the rst time. What's more, the experimen-
tal data were correlated with the Wilson and NRTL models and also
predicted by the original UNIFAC model.
2. Experimental
2.1. Materials
2-methylthiophene was purchased from Aladdin Chemistry Co. Ltd.
(Shanghai, China). n-Heptane and 2,2,4-trimethylpentane were obtain-
ed from Shanghai Crystal Pure Industrial Co. Ltd. n-Octane and n-Decane
were supplied by Alfa Aesar. The purities and water contents of all the
chemical reagent were checked by using gas chromatography (GC)
equipped with a ame ionization detector (FID) and Abbe refractome-
ter, respectively. The corresponding results were given in Table 1. In ad-
dition, the boiling points of pure substances at 101.33 kPa were

http://dx.doi.org/10.1016/j.molliq.2016.09.114
0167-7322/ 2016 Elsevier B.V. All rights reserved.
126 J. Li et al. / Journal of Molecular Liquids 224 (2016) 125131

Table 1
Purity, water content and boiling temperature of pure components.

Component Purity (mol%) Water Boiling temperature, Tb

(mass%) (K)

Suppliers GC Experimental Literaturea

2-Methylthiophene N99.5 99.76 0.02 385.82 385.71

n-HEPTANE N99.5 99.83 0.02 371.66 371.55
2,2,4-Trimethylpentane N99.5 99.54 0.02 372.48 372.39
n-Nonane N99.5 99.63 0.02 423.84 423.97
n-Decane N99.5 99.61 0.02 447.23 447.31
a
Taken from Aspen properties databank.

determined by using the modied Rose-Williams still, the experimental

data and the calculated values based on Antoine equation for theses
compounds were also listed in Table 1.

2.2. Apparatus and procedures

Fig. 2. Vapor pressure for n-heptane. , from this work; , from the literature [15]; ,
The VLE measurements were carried out in a modied Rose-Wil- calculated by the Antoine equation with the parameters in the Aspen properties databank.

liams still (Beiyang Analytical Instrument Company), which was

exbibited in Fig. 1. In a typical experiment, rstly the pure component
1 was introduced to the still and its boiling point was determined.
Then the component 2 was added to the still until the content of the
component 2 in the still was increased to 100% at intervals by a syringe.
Both the vapor and liquid phases were continuously circulating to pro-
vide intimate contact of the phases and ensure that equilibrium could be
established rapidly. In each experiment, equilibrium was assumed
when the equilibrium temperature was maintained constant for N
60 min, and the vapor and liquid samples were withdrawn simulta-
neously to be analyzed under the equilibrium temperature.
The temperature were measured by using a precise mercury ther-
mometer whose uncertainty is 0.02 K. Meanwhile, the pressure of
the system was controlled by using a U-shaped differential manometer
(Nanjing Hengyuan Automatic Gauge Company) whose uctuation was
held within 0.03 kPa with a two-step automatic control system. Water
was used as the condensation liquid.

2.3. Analysis and GC calibration

The vapor (cooled to liquid) and liquid compositions were analyzed

by a GC (model:GC-950, Haixin Analytical Instrument Company)
equipped with a FID. The GC column used was an OV-101capillary col-
umn (30 m 0.25 mm 0.50 m). The FID and injector were set at
240 C. High purity nitrogen (99.999%) was used as the carrier gas at a
constant ow rate of 30 mL/min. The detector was connected to a
CDMC-21 chromatograph work station. The initial column temperature
was held at 90 C for 2 min and then increased to 230 C at a rate of
20 C/min and then held at 230 C for 2 min. In order to ensure the ac-
curacy, each sample was analyzed at least three times, and the uncer-
tainties of the mole fractions were 0.001. The pure components were
used to determine the retention times, after that the GC was calibrated
with 12 mixtures of known composition that were prepared gravimet-
rically to determine the response factors for the binary system.

Table 2
Pure component vapor pressures of n-heptane.

T (K) Pexp (kPa) Pcala (kPa) P(kPa)

370.27 97.32 97.47 0.15

369.99 96.57 96.67 0.10
369.66 95.43 95.73 0.30
368.78 93.21 93.25 0.04
368.04 91.35 91.20 0.15
367.57 90.03 89.92 0.11
367.48 89.36 89.68 0.32
367.20 88.54 88.93 0.39
366.47 86.78 86.98 0.20
Fig. 1. Rose-Williams VLE device. 1, heating column; 2, liquid sample connection; 3, a
365.19 83.49 83.66 0.17
precise mercury thermometer; 4, condenser; 5, condensate; 6, contact with pressure-
363.80 80.25 80.16 0.09
controlling devices; 7, vapor (cooled to liquid) sample connection. (For interpretation of
a
the references to colour in this gure legend, the reader is referred to the web version of Using the pure component vapor pressure equation parameters (A, B, C, D, E and F) for
this article.) the Antoine Equation from the Aspen properties databank .
 J. Li et al. / Journal of Molecular Liquids 224 (2016) 125131 127

Table 3
VLE data for the binary systems at 90.00 kPaa.

NO. T(K) x1 y1 1 2 Calculated by Wison Calculated by NRTL

Tb/K yb1 Tb/K yb1

n-Heptane (1) + 2-Methylthiophene (2) system

1 367.51 1.0000 1.0000 1.00 0.06 0.0000 0.06 0.0000
2 367.64 0.9543 0.9624 1.01 1.26 0.03 0.0047 0.09 0.0079
3 367.76 0.8734 0.8981 1.02 1.23 0.15 0.0116 0.11 0.0156
4 367.89 0.8216 0.8455 1.02 1.32 0.22 0.0027 0.08 0.0051
5 368.19 0.7476 0.7742 1.02 1.35 0.27 0.0084 0.05 0.0098
6 368.62 0.6701 0.7150 1.03 1.28 0.30 0.0070 0.02 0.0127
7 369.19 0.5864 0.6559 1.07 1.21 0.33 0.0022 0.05 0.0115
8 369.59 0.5429 0.6258 1.09 1.18 0.30 0.0007 0.05 0.0099
9 370.42 0.4566 0.5760 1.16 1.10 0.30 0.0169 0.14 0.0058
10 370.99 0.4091 0.5275 1.16 1.10 0.27 0.0057 0.16 0.0042
11 371.79 0.3577 0.4788 1.18 1.09 0.14 0.0011 0.11 0.0085
12 372.55 0.2998 0.4384 1.26 1.05 0.21 0.0084 0.27 0.0053
13 374.29 0.2081 0.3448 1.36 1.03 0.15 0.0046 0.34 0.0107
14 375.32 0.1659 0.2892 1.39 1.03 0.09 0.0026 0.31 0.0080
15 376.31 0.1291 0.2433 1.46 1.02 0.08 0.0009 0.29 0.0130
16 377.32 0.0981 0.1963 1.50 1.01 0.04 0.0023 0.19 0.0130
17 380.05 0.0318 0.0730 1.60 1.00 0.06 0.0035 0.28 0.0061
18 381.61 0.0000 0.0000 1.00 0.01 0.0000 0.01 0.0000

2,2,4-trimethylpentane (1) + 2-Methylthiophene (2) system

1 367.95 1.0000 1.0000 1.01 0.16 0.0000 0.16 0.0000
2 367.90 0.9348 0.9332 1.00 1.56 0.06 0.0008 0.08 0.0004
3 367.97 0.8895 0.8928 1.01 1.47 0.03 0.0033 0.00 0.0029
4 368.02 0.8442 0.8502 1.01 1.46 0.05 0.0008 0.02 0.0006
5 368.04 0.8048 0.8195 1.02 1.40 0.01 0.0031 0.02 0.0031
6 368.17 0.7628 0.7852 1.03 1.37 0.02 0.0024 0.00 0.0027
7 368.56 0.6743 0.7156 1.05 1.30 0.05 0.0006 0.03 0.0002
8 368.96 0.5803 0.6554 1.10 1.21 0.10 0.0060 0.12 0.0071
9 369.47 0.5274 0.6077 1.11 1.20 0.01 0.0045 0.02 0.0033
10 369.93 0.4588 0.5623 1.16 1.15 0.16 0.0013 0.16 0.0003
11 370.46 0.4074 0.5232 1.20 1.13 0.19 0.0027 0.19 0.0019
12 371.16 0.3449 0.4768 1.27 1.10 0.29 0.0007 0.27 0.0002
13 372.27 0.2797 0.4226 1.34 1.06 0.21 0.0008 0.19 0.0009
14 373.66 0.2347 0.3804 1.38 1.03 0.27 0.0016 0.30 0.0015
15 375.51 0.1601 0.2947 1.49 1.01 0.35 0.0001 0.38 0.0007
16 376.38 0.1258 0.2496 1.57 1.00 0.23 0.0009 0.26 0.0003
17 377.09 0.0986 0.2111 1.66 1.00 0.05 0.0039 0.08 0.0032
18 378.97 0.0550 0.1323 1.77 0.99 0.17 0.0034 0.19 0.0028
19 380.13 0.0299 0.0774 1.85 0.99 0.15 0.0021 0.16 0.0018
20 381.61 0.0000 0.0000 1.00 0.01 0.0000 0.01 0.0000

n-Nonane (1) + 2-Methylthiophene (2)

1 381.61 0.0000 0.0000 1.00 0.01 0.0000 0.01 0.0000
2 382.88 0.0684 0.0291 1.32 1.00 0.10 0.0002 0.10 0.0003
3 384.34 0.1363 0.0571 1.25 1.01 0.05 0.0008 0.05 0.0006
4 385.38 0.1794 0.0753 1.20 1.01 0.05 0.0015 0.05 0.0012
5 386.97 0.2537 0.1067 1.14 1.02 0.03 0.0041 0.03 0.0036
6 389.02 0.3413 0.1536 1.09 1.04 0.10 0.0006 0.11 0.0000
7 390.04 0.3815 0.1717 1.07 1.07 0.13 0.0040 0.13 0.0034
8 392.41 0.4571 0.2203 1.00 1.08 0.09 0.0001 0.09 0.0006
9 393.93 0.5085 0.2481 1.01 1.09 0.06 0.0058 0.05 0.0053
10 395.68 0.5632 0.2876 1.02 1.10 0.01 0.0063 0.01 0.0058
11 398.49 0.6376 0.3534 1.01 1.12 0.08 0.0038 0.08 0.0033
12 400.86 0.6944 0.4095 1.00 1.14 0.11 0.0046 0.11 0.0043
13 403.04 0.7417 0.4652 1.00 1.15 0.14 0.0039 0.15 0.0036
14 404.68 0.7752 0.5096 1.00 1.16 0.14 0.0036 0.15 0.0032
15 406.87 0.8173 0.5741 1.00 1.18 0.10 0.0017 0.12 0.0012
16 409.06 0.8567 0.6416 1.00 1.19 0.02 0.0016 0.04 0.0012
17 412.06 0.9044 0.7359 1.00 1.23 0.02 0.0035 0.01 0.0031
18 415.79 0.9577 0.8685 1.00 1.26 0.13 0.0027 0.12 0.0024
19 418.34 0.9904 0.9667 1.00 1.32 0.21 0.0018 0.20 0.0017
20 419.19 1.0000 1.0000 1.01 0.18 0.0000 0.18 0.0000

n-Decane (1) + 2-Methylthiophene (2)

1 381.62 0.0000 0.0000 1.00 0.00 0.0000 0.00 0.0000
2 382.73 0.0528 0.0115 1.43 1.01 0.20 0.0001 0.26 0.0005
3 385.44 0.1548 0.0271 1.04 1.03 0.10 0.0040 0.28 0.0044
4 387.90 0.2367 0.0444 1.02 1.05 0.02 0.0038 0.22 0.0048
5 390.83 0.3192 0.0659 1.01 1.06 0.15 0.0029 0.02 0.0041
6 394.44 0.4112 0.1055 1.10 1.06 0.14 0.0075 0.06 0.0066
7 396.76 0.4649 0.1234 1.05 1.07 0.08 0.0043 0.05 0.0038
8 399.89 0.5302 0.1477 0.99 1.09 0.01 0.0025 0.02 0.0025
9 402.54 0.5757 0.1702 0.97 1.10 0.11 0.0065 0.16 0.0061

(continued on next page)

128 J. Li et al. / Journal of Molecular Liquids 224 (2016) 125131

Table 3 (continued)

NO. T(K) x1 y1 1 2 Calculated by Wison Calculated by NRTL

Tb/K yb1 Tb/K yb1

10 407.32 0.6525 0.2279 0.98 1.11 0.07 0.0056 0.15 0.0046

11 410.50 0.6979 0.2638 0.96 1.12 0.04 0.0123 0.12 0.0111
12 412.17 0.7207 0.2946 0.98 1.12 0.02 0.0063 0.06 0.0051
13 414.78 0.7533 0.336 0.99 1.12 0.04 0.0050 0.02 0.0038
14 416.50 0.774 0.3607 0.98 1.13 0.08 0.0090 0.03 0.0079
15 420.36 0.8164 0.4272 0.98 1.14 0.11 0.0109 0.09 0.0101
16 428.31 0.8919 0.5991 1.00 1.13 0.14 0.0039 0.16 0.0041
17 434.50 0.9423 0.7487 0.99 1.16 0.15 0.0085 0.19 0.0093
18 437.06 0.9616 0.8273 1.00 1.13 0.19 0.0019 0.23 0.0028
19 440.14 0.9834 0.9199 1.00 1.14 0.21 0.0013 0.23 0.0019
20 442.95 1.0000 1.0000 1.00 0.08 0.0000 0.08 0.0000
a
u(T) = 0.02 K, and u(x1) = u(y1) = 0.001.

3. Results and discussion 3.3. Thermodynamic consistency test

3.1. Reliability test of the instruments In order to test the thermodynamic consistency, the semi-empirical
method proposed by Herington was applied to determine the measured
In order to determine the reliability of the modied Rose-Williams
still, the vapor pressure values for the pure n-Heptane were measured
under the different temperatures. Which were also compared with the
calculated values by using the Antoine equation and the reference, re-
spectively. As exhibited in the Fig. 2 and Table 2, it could be seen that
the experimental data in this work could be corrected well by using
the Antoine equation with the parameters in the Aspen properties
databank. The determined values were also consistent with the open lit-
erature [7]. Therefore, the experimental instrument used in this work is
reliable.

3.2. Vapor-liquid equilibrium measurements

The experimental vapor-liquid equilibrium data for the four binary

systems (n-heptane + 2-methylthiophene, 2,2,4-trimethylpentane +
2-methylthiophene, n-nonane + 2-methylthiophene, n-decane + 2-
methylthiophene) were given in Table 3, and the T-x1-y1 diagrams
were displayed in Figs. 36, respectively. From the gures it can be
found that the homogeneous azeotropic behavior existed in the 2,2,4-
trimethylpentane + 2-methylthiophene system. While the azeotropic
Fig. 4. Temperature-composition diagram for the 2,2,4-trimethylpentane (1) + 2-
behavior was not found in the other three binary systems. methylthiophene (2) system at 90.00 kPa. , x-T from experimental data; , y-T from
experimental data; , from Wilson model; , from NRTL model;, from original
UNIFAC model.

Fig. 3. Temperature-composition diagram for the n-heptane (1) + 2-methylthiophene (2) Fig. 5. Temperature-composition diagram for the n-nonane (1) + 2-methylthiophene (2)
system at 90.00 kPa. , x-T from experimental data; , y-T from experimental data; , system at 90.00 kPa. , x-T from experimental data; , y-T from experimental data; ,
from Wilson model; , from NRTL model;, from original UNIFAC model. from Wilson model; , from NRTL model;, from original UNIFAC model.
 J. Li et al. / Journal of Molecular Liquids 224 (2016) 125131 129

Table 6
Physical properties and parameters of pure componentsa.

Properties 2-Methylthiophene n-Heptane 2,2,4-trimethylpentane

n-Nonane n-Decane

MW 98.17 100.20 114.23 128.26 142.28

TB(K) 385.71 371.58 372.39 423.97 443.31
Tc(K) 609.00 540.20 543.80 594.60 617.70
Pc(MPa) 4.91 2.74 2.57 2.29 2.11
Vc (ml mol1) 275.00 428.00 468.00 551.00 617.00
Zc 0.267 0.261 0.266 0.255 0.254
0.239 0.349 0.303 0.443 0.492
a
Taken from Aspen properties databank.

3.4. Correlations for the VLE data

The activity coefcients i were calculated from the Eq. 2:

^ Z P Si
yi P i V Li
Fig. 6. Temperature-composition diagram for the n-decane (1) + 2-methylthiophene(2) i s s exp dP 2
xi P i i P RT
system at 90.00 kPa. , x-T from experimental data; , y-T from experimental data; ,
from Wilson model; , from NRTL model;, from original UNIFAC model.

experimental VLE data and the corresponding criterion is (DJ) b 10 [8].
The corresponding results were given in Table 4.
For the purpose of checking the reliability of each measured point, all
the experimental data were also conrmed by using the Van Ness meth-
od at the same time. The relative criterion for the van Ness method
could be expressed as Eq. 1 [9]:
1X N
1X N  
 
y y 100yi exp yi cal 
N i1 N i1
where N is the experimental data point number; the superscripts cal
and exp are the calculated and experimental values, respectively. The
Wilson model was used to get the yi exp . If y b 1, the measured point
can be considered to pass the thermodynamic consistency test. The
checking results for the n-heptane + 2-methylthiophene, 2,2,4-
trimethylpentane + 2-methylthiophene, n-nonane + 2-
methylthiophene, n-decane + 2-methylthiophene were 0.46, 0.20,
0.25 and 0.48, respectively.
The above results indicated that all the measurements in this work
passed the consistency test.
where yi and xi are the mole fraction of component i in the vapor phase
and liquid phase, respectively; P and Psi are the total pressure of the sys-
tem and the vapor pressure of pure component i at the system temper-
^ and si are the fugacity coefcient of the
ature, respectively; i
component i in the vapor phase and the saturated liquid fugacity coef-
cient of the pure component i at the system temperature T, respectively.
VLi is the molar volume of pure component i in the liquid phase at the
system temperature and pressure, T is temperature in Kelvin, and R is
the universal gas constant (8.31441 JK1mol1).
The Soave-Redlich-Kwong [10] equation of state with quadratic
1 mixing rules in the attractive parameter and linear in co-volume was
^ and si . The liquid
used to calculate vapor phase fugacity coefcient i
molar volume VLi could be calculated by using the Rackett equation
[11]. The saturated vapor pressure of the pure component could be
also calculated by using the extended Antoine equation, Eq. 3:
ln ps =kPa A1 B2 =T C 3 D4 T E5 ln T F 6 T G7 for T L bTbT U 3
The extended Antoine parameters of the pure substances were
shown in Table 5. The values of molecular weight, bubble point temper-
ature, critical temperature, critical pressure, critical volume and acentric
factor were presented in Table 6.

Table 4
Thermodynamic consistency test results.

Systems Herington Van Ness

D J D-J y

n-Heptane (1) + 2-Methylthiophene (2) 7.93 5.75 2.18 0.46

2,2,4-trimethylpentane(1) + 2-Methylthiophene (2) 4.11 5.57 1.46 0.20
n-Nonane(1) + 2-Methylthiophene (2) 13.38 14.77 1.39 0.25
n-Decane (1) + 2-Methylthiophene (2) 28.43 24.11 4.32 0.48

Table 5
Paremeters of the extended Antoine equationa.

Component A1 B2 C3 D4 E5 F6 G7 TL/K TU/K

6
2-Methylthiophene 88.50 7619.30 0.00 0.00 10.95 7.39 10 2.00 209.79 609.00
n-Heptane 80.92 6996.40 0.00 0.00 9.88 7.21 106 2.00 182.57 540.20
2,2,4-Trimethylpentane 78.00 6722.20 0.00 0.00 9.52 7.22 106 2.00 165.78 543.80
n-Nonane 102.44 9030.40 0.00 0.00 12.88 7.85 106 2.00 219.66 594.60
n-Decane 105.82 9749.60 0.00 0.00 13.25 7.13 106 2.00 243.51 617.70
a
Taken from Aspen properties databank.
130 J. Li et al. / Journal of Molecular Liquids 224 (2016) 125131

Table 7
Corrected binary interactions parameters and root-mean-square deviations between experimental and calculated values for the four binary systems with Wilson, NRTL and original
UNIFAC models.

Systema 1 2 3 4

Wilson
b12(K) 286.44 460.18 136.20 637.35
b21(K) 62.51 192.64 23.80 284.93
Tb/K 0.20 0.16 0.10 0.12
yb1 0.0063 0.0178 0.0143 0.0468
c1 0.0193 0.0083 0.0136 0.0464

NRTL
g12g22(J mol1) 48.60 380.13 66.97 337.50
g21g11(J mol1) 147.28 80.79 181.52 667.89
Tb/K 0.18 0.17 0.11 0.15
yb1 0.0092 0.0182 0.0127 0.0521
yc1 0.0508 0.0088 0.0150 0.0503

original UNIFAC
Tb/K 0.19 0.18 0.16 0.14
yb1 0.0076 0.0182 0.0327 0.0878
c1 0.0272 0.0125 0.0352 0.0929
a
System 14 represents n-Heptane(1) + 2-Methylthiophene(2), 2,2,4-trimethylpentane(1) + 2-Methylthiophene(2), n-Nonane(1) + 2-Methylthiophene(2), n-Decane (1) + 2-
Methylthiophene (2), respectively.
b

c
.
.

3.5. Correlations and predictions for the VLE data in Figs. 3 to 6. The root-mean- squared relative deviations of the exper-
imental and calculated vapor phase mole fraction y1 with the activity
The liquid phase activity coefcients i were correlated by using the coefcients and the absolute deviations for the equilibrium temperature
Wilson model and NRTL model, respectively. The objective function OF T were also summarized in Table 7.
used for determining the interaction parameters bij in the Wilson Meanwhile, the deviations of the experimental and calculated tem-
model with gij gii in the NRTL model, and the relative deviations perature change T and vapor phase mole fraction y1 for the four bi-
from the activity coefcients were given by Eq. 4, respectively. Where nary system were also listed in Table 8. As can be seen from the table
N was the number of experimental points, and the subscripts cal and that the experimental data were well correlated with each of the three
exp represented calculated and experimental values, respectively. models. The maximum absolute deviation of the temperature was
0.43 K, and the average absolute deviations of the temperature for all
(   )
X
N X
m
y cal y exp  2  the systems were below 0.17 K. The maximum relative deviation of
i i cal exp
OF exp
T i =KT i =K 4 the vapor phase mole fraction was 0.0878 by using origin UNIFAC re-
k1 i1
yi
gression model, and the average absolute deviations of the vapor com-
positions for all the systems were below 0.0099.
The values of bij, gij gii and i et al. for the four binary systems According to the above analysis, it can be concluded that a good
were obtained by the regression and were listed in Table 7. The root- agreement can be got between the experimental and calculated values.
mean-squared relative deviations of the vapor phase mole fraction y1 Therefore, the measured VLE data in this work were successfully corre-
with the activity coefcients and the absolute deviations of the equilib- lated by using the Wilson and NRTL models. The Original UNIFAC model
rium temperature T between the experimental and calculated data for also gave better predictions for the four binary systems.
these four binary systems were also listed in Table 7. It can be seen that
good agreement between measurements and models were achieved for 4. Conclusions
all the systems. The original UNIFAC method was also used to predict
the VLE data for the four systems with the T-x1-y1 diagrams displayed The isobaric VLE data for four systems of 2-methylthiophene with n-
heptane,
2,2,4-trimethylpentane, n-nonane, and n-decane were determined
Table 8
Deviations of temperature change(T) and vapor mole fractions change(y1) between at 90.00 kPa with a modied Rose-Williams still. The azeotropic behav-
the calculated and the experimental values using the Wilson, NRTL and original UNIFAC ior was found in the 2,2,4-trimethylpentane + 2-methylthiophene sys-
equations at 90.00 kPa. tem. All the experimental data were checked with the Herington
Systems Wilson NRTL original UNIFAC
method and the Van Ness test, which passed the thermodynamic con-
sistency tests. The experimental data were correlated well by using
T/K y1 T/K y1 T/K y1
the Wilson and NRTL models with the root-mean-squared relative devi-
1 Ave 0.17 0.0046 0.14 0.0082 0.15 0.0053 ations of 1 0.0521 and the absolute deviations of T 0.20. Mean-
Max 0.33 0.0169 0.34 0.0156 0.32 0.0208
while, the corresponding binary interaction parameters were also
2 Ave 0.13 0.0020 0.13 0.0017 0.14 0.0036
Max 0.35 0.0045 0.38 0.0033 0.43 0.0063 obtained by using the Wilson and NRTL activity coefcient models.
3 Ave 0.09 0.0025 0.09 0.0022 0.14 0.0068 The Original UNIFAC model was also used to predict the VLE data and
Max 0.21 0.0063 0.20 0.0058 0.29 0.0136 gave better prediction results. The measured VLE data and the obtained
4 Ave 0.10 0.0048 0.12 0.0047 0.12 0.0099 interaction parameters can be used for the design and simulation of the
Max 0.21 0.0123 0.28 0.0111 0.28 0.0211
deep desulfurization processes.
 J. Li et al. / Journal of Molecular Liquids 224 (2016) 125131
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