Article

pubs.acs.org/jced

Isobaric Vapor−Liquid Equilibrium for Binary Systems of

Cyclohexanone + Benzene, Cyclohexanone + Toluene, and
Cyclohexanone + p‑Xylene at 101.3 kPa
Jun Gao, Kai Zhang, Dongmei Xu,* Lianzheng Zhang, Nannan Chen, and Chunlu Li
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
*
S Supporting Information

ABSTRACT: The isobaric vapor−liquid equilibrium (VLE) data for the cyclohexanone +
benzene, cyclohexanone + toluene, and cyclohexanone + p-xylene systems at a pressure of 101.3
kPa were measured with a modified Rose-type recirculating still. The thermodynamic
consistency of the experimental data was checked with the Herington, Van Ness, infinite
dilution, and pure-component consistency tests. In addition, the VLE data were correlated by
the nonrandom two-liquid (NRTL), Universal Quasichemical (UNIQUAC), and Wilson
activity coefficient models, and the binary interaction parameters for the three thermodynamic
models were regressed. The calculated results for the three models show good agreement with
the experimental data. The UNIFAC model was also used to predict the VLE data and
presented good results for the three systems.

1. INTRODUCTION
Cyclohexanone is an important raw material in the chemical
industry.1 2-(1-Cyclohexen-1-yl)cyclohexanone (D2) and 2-
cyclohexylidenecyclohexanone (D3) can be synthesized by self-
condensation of cyclohexanone and are important intermedi-
ates in the synthesis of o-phenylphenol (OPP).2 OPP is an
important fine-chemical industrial product and is widely used to
synthesis surfactants, antiseptics, printing and dyeing assistants,
and plastic thermal stabilizers.3
The self-condensation of cyclohexanone can be performed
using a catalyst of aluminum oxide. Compared with the
traditional acid4 and alkali5 catalysts, aluminum oxide has better
catalytic activity and selectivity, causes less corrosion on the
equipment, and is more environmental friendly. In the
cyclohexanone self-condensation, the reaction mixture consists
of aluminum oxide, unreacted cyclohexanone, D2, and D3.
After filtration, a solid mixture of aluminum oxide with a certain
amount of organic compounds was obtained. To recover and
reutilize the aluminum oxide, benzene, toluene, and p-xylene
have been selected as solvents to dissolve the organics. The
aluminum oxide catalyst is separated by the filtration.
Meanwhile, the solvents are recovered by distillation from the
mixture consisting of cyclohexanone, D2, and D3 after the
filtration process. Therefore, the vapor−liquid equilibrium
(VLE) data for the solvent + cyclohexanone systems are needed
for the design and simulation of the distillation process.
Previously, the isothermal VLE data for the cyclohexanone +
benzene system at 298.15 K were reported by Matteoli and
Lepori.6 The VLE data for cyclohexanone + p-xylene at 40 and
98.67 kPa were determined by Comelli and Francesconi.7
Kireev et al.8 reported the VLE data for the cyclohexanone +
toluene system at 101.33 kPa in 1952, but the full text of their
article cannot be retrieved. However, the VLE data for the
cyclohexanone + benzene and cyclohexanone + p-xylene binary
systems at 101.3 kPa have not been found in the Dortmund
Data Bank (DDB) and the National Institute of Standards and
Technology (NIST) database.
In the present work, the isobaric VLE data for the
cyclohexanone + benzene, cyclohexanone + toluene, and
cyclohexanone + p-xylene systems at a pressure of 101.3 kPa
were measured with a modified Rose-type recirculating still.
The Herington method,9 Van Ness method,10 infinite dilution
test,11 and pure-component consistency test12 were applied to
check the thermodynamic consistency of the VLE data. The
VLE data for the three binary systems were correlated by the
nonrandom two-liquid (NRTL),13 Universal Quasichemical
(UNIQUAC),14 and Wilson15 activity coefficient models.
Additionally, the UNIFAC16 model was used to predict the
VLE data for the three systems.
2. EXPERIMENTAL SECTION
2.1. Materials. All of the chemicals used in this work were
analytical grade and obtained commercially. The relevant
detailed information about the chemical reagents is listed in
Table 1. The purities of cyclohexanone, benzene, toluene, and
p-xylene were checked by gas chromatography (SP6890,
Shandong Lunan Rui Hong Chemical Instrument Co., Ltd.).
All of the chemicals were used without any further purification.
2.2. Apparatus and Procedures. The VLE data for the
cyclohexanone + benzene, cyclohexanone + toluene, and
cyclohexanone + p-xylene systems at pressure of 101.3 kPa
were measured with a modified Rose-type recirculating still,
which was described detail in the previous work at 101.3
Received: October 11, 2016
Accepted: June 9, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.6b00877

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 1. Chemical Description

component formula CAS no. supplier mass fraction analysis method
cyclohexanone C6H10O 108-94-1 Tianjin Fuyu Fine Chemical Co., Ltd. 0.995 GCa
benzene C6H6 71-43-2 Tianjin Fuyu Fine Chemical Co., Ltd. 0.995 GCa
toluene C7H8 108-88-3 Tianjin Fuyu Fine Chemical Co., Ltd. 0.995 GCa
p-xylene C8H10 106-42-3 Chengdu Kelong Chemical Co., Ltd. 0.990 GCa
a
Gas chromatography.

Table 2. Experimental Isobaric VLE Data and Correlation Results for the Cyclohexanone + Benzene, Cyclohexanone + Toluene,
and Cyclohexanone + p-Xylene Systems at 101.3 kPaa
NRTL UNIQUAC Wilson UNIFAC
T/K x1 y1 γ1 γ2 ΔT/K Δy1 ΔT/K Δy1 ΔT/K Δy1 ΔT/K Δy1
Cyclohexanone (1) + Benzene (2)
356.30 0.1106 0.0115 1.0668 1.0134 0.01 0.0002 0.15 0.0004 0.06 0.0002 0.06 0.0009
360.15 0.2438 0.0249 0.8998 1.0482 0.06 0.0011 0.12 0.0010 0.09 0.0018 0.12 0.0025
362.65 0.3124 0.036 0.9215 1.0594 0.03 0.0001 0.11 0.0003 0.16 0.0012 0.04 0.0010
367.25 0.4155 0.0573 0.9266 1.0689 0.04 0.0009 0.11 0.0005 0.23 0.0013 0.08 0.0004
373.60 0.526 0.093 0.9420 1.0645 0.05 0.0016 0.09 0.0007 0.16 0.0016 0.07 0.0017
379.50 0.6064 0.1324 0.9455 1.0486 0.10 0.0010 0.13 0.0020 0.10 0.0033 0.03 0.0005
386.40 0.6841 0.1904 0.9548 1.0225 0.08 0.0001 0.12 0.0033 0.01 0.0053 0.08 0.0020
391.90 0.7385 0.2459 0.9554 1.0050 0.09 0.0043 0.05 0.0073 0.21 0.0099 0.29 0.0078
398.90 0.7966 0.3365 0.9737 0.9631 0.06 0.0028 0.03 0.0055 0.14 0.0079 0.23 0.0080
403.85 0.8339 0.4131 0.9834 0.9314 0.04 0.0017 0.02 0.0040 0.07 0.0055 0.15 0.0073
408.20 0.8652 0.4877 0.9847 0.9092 0.08 0.0040 0.06 0.0059 0.03 0.0060 0.11 0.0094
412.90 0.8979 0.5849 0.9948 0.8780 0.15 0.0026 0.14 0.0038 0.03 0.0022 0.10 0.0067
419.25 0.9396 0.7368 1.0042 0.8230 0.12 0.0020 0.11 0.0016 0.06 0.0051 0.01 0.0003
423.75 0.9682 0.8621 1.0102 0.7467 0.01 0.0091 0.01 0.0092 0.13 0.0126 0.10 0.0089
Cyclohexanone (1) + Toluene (2)
384.00 0.0096 0.0048 1.8580 0.9998 0.01 0.0002 0.01 0.0001 0.02 0.0001 0.01 0.0000
384.85 0.0573 0.0224 1.4120 1.0072 0.02 0.0004 0.06 0.0002 0.08 0.0002 0.03 0.0002
386.45 0.1397 0.0458 1.1229 1.0299 0.12 0.0004 0.16 0.0001 0.16 0.0004 0.07 0.0001
389.55 0.2781 0.0898 0.9993 1.0743 0.04 0.0028 0.04 0.0015 0.10 0.0002 0.16 0.0013
394.95 0.4362 0.1589 0.9491 1.0983 0.16 0.0020 0.00 0.0019 0.02 0.0050 0.05 0.0006
400.25 0.5585 0.2411 0.9549 1.1013 0.12 0.0007 0.02 0.0037 0.06 0.0064 0.02 0.0016
401.35 0.581 0.2625 0.9667 1.0963 0.12 0.0030 0.03 0.0014 0.09 0.0039 0.03 0.0006
403.55 0.6251 0.3032 0.9715 1.0945 0.08 0.0025 0.02 0.0017 0.09 0.0038 0.02 0.0001
405.75 0.667 0.35 0.9847 1.0875 0.02 0.004 0.00 0.0010 0.07 0.0007 0.00 0.0021
410.95 0.7573 0.4662 0.9936 1.0779 0.06 0.0031 0.02 0.0013 0.04 0.0005 0.02 0.0006
416.15 0.8365 0.5967 0.9947 1.0673 0.02 0.0006 0.06 0.0006 0.08 0.0001 0.08 0.0015
419.25 0.8815 0.686 0.9965 1.0662 0.06 0.0011 0.02 0.0004 0.00 0.0012 0.06 0.0026
421.95 0.9186 0.771 0.9991 1.0637 0.09 0.0015 0.03 0.0004 0.06 0.0013 0.03 0.0020
427.55 0.9886 0.9638 1.0010 1.0582 0.06 0.0005 0.04 0.0001 0.06 0.0005 0.02 0.0001
Cyclohexanone (1) + p-Xylene (2)
411.55 0.0195 0.0196 1.5948 0.9989 0.05 0.0001 0.06 0.0001 0.07 0.0001 0.05 0.0001
411.85 0.125 0.0998 1.2560 1.0195 0.03 0.0001 0.03 0.0004 0.04 0.0020 0.03 0.0004
413.25 0.2706 0.1895 1.0589 1.0610 0.05 0.0012 0.05 0.0011 0.04 0.0013 0.04 0.0014
414.85 0.3979 0.2760 1.0028 1.1007 0.05 0.0017 0.05 0.0022 0.04 0.0048 0.07 0.0017
416.65 0.5034 0.3636 0.9933 1.1192 0.04 0.0005 0.04 0.0001 0.01 0.0037 0.06 0.0006
417.05 0.5245 0.3839 0.9955 1.1199 0.04 0.0019 0.04 0.0013 0.00 0.0023 0.06 0.0020
418.25 0.5819 0.4391 0.9930 1.1242 0.00 0.0025 0.02 0.0019 0.06 0.0016 0.01 0.0024
419.65 0.6485 0.5079 0.9921 1.1318 0.03 0.0016 0.02 0.0012 0.03 0.0020 0.03 0.0013
420.45 0.6824 0.5463 0.9923 1.1316 0.00 0.0017 0.01 0.0013 0.05 0.0016 0.00 0.0012
421.95 0.747 0.6251 0.9961 1.1300 0.04 0.0020 0.03 0.0018 0.01 0.0005 0.02 0.0014
423.05 0.7885 0.6793 0.9958 1.1248 0.03 0.0019 0.04 0.0017 0.06 0.0001 0.05 0.0013
423.35 0.8025 0.6984 0.9979 1.1243 0.02 0.0020 0.01 0.0019 0.01 0.0002 0.01 0.0014
425.05 0.865 0.785 0.9948 1.1239 0.06 0.0003 0.06 0.0005 0.07 0.0015 0.10 0.0009
425.75 0.896 0.8322 0.9995 1.1191 0.04 0.0003 0.04 0.0001 0.04 0.0006 0.01 0.0002
426.75 0.9311 0.8862 0.9978 1.1177 0.02 0.0005 0.02 0.0007 0.02 0.0011 0.05 0.0009
a
The standard uncertainties u of T, p, x1, and y1 are u(T) = 0.1 K, u(p) = 0.1 kPa, and u(x) = u(y) = 0.001.

B DOI: 10.1021/acs.jced.6b00877
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

kPa.17−19 In the recirculating still, both liquid and condensed

vapor phases were continuously recirculated to ensure that they
were in intimate contact. The equilibrium temperature was
ascertained and recorded when the temperature was kept
constant for 60 min.20 Then the samples of the vapor and liquid
phases were withdrawn by syringe for analysis.
The gas chromatograph (SP6890, Shandong Lunan Rui
Hong Chemical Instrument Co., Ltd.) was equipped with a
thermal conductivity detector, and the column used was a
capillary column (DB-624, 30 m × 0.53 m × 3 μm). The
detector was connected to an N2000 gas chromatography
workstation developed by Zhejiang University. The gas
chromatograph was calibrated with standard solutions that
were prepared gravimetrically using an AR1140 electronic
balance (Ohaus Corporation), and the uncertainty was 0.0001
g. The mole components obtained by GC were compared with
those obtained by mass, and the absolute deviation was no
greater than 0.001 in mole fraction. The gas carrier was high- Figure 1. T−x−y phase equilibrium for the cyclohexanone (1) +
purity hydrogen ( mass-fraction purity > 0.9999), and the flow benzene (2) system at 101.3 kPa: ●, x, T experimental data; ○, y, T
rate was controlled at 20 mL·min−1. The inlet pressure of the experimental data; solid line, correlated results by the NRTL model;
column was kept at 0.15 MPa. The temperatures of the injector, dashed line, correlated results by the UNIQUAC model; dashed-
detector, and oven were kept at 433.15, 433.15, and 403.15 K, dotted line, correlated results by the Wilson model. dotted line,
respectively. Each sample was analyzed at least three times to predicted results by the UNIFAC model.
ensure the accuracy. The temperature was measured with an
accurate mercury thermometer (Tianjin Glass Instrument
Factory) with an uncertainty of ±0.1 K. The pressure was
maintained at 101.3 kPa by a U-shaped differential manometer,
and the fluctuations were held within 0.1 kPa by a two-step
automatic control system.

3. RESULTS AND DISCUSSION

3.1. Experimental Data. The measured isobaric vapor−
liquid equilibrium data (T, xi, yi) and the calculated activity
coefficients (γi) of each constituent at 101.3 kPa for the
cyclohexanone (1) + benzene (2), cyclohexanone (1) + toluene
(2), and cyclohexanone (1) + p-xylene (2) binary systems are
listed in Table 2. Furthermore, the T−x−y phase diagrams for
the three binary systems are presented in Figures 1 to 3. No
azeotropic behavior was found for the three binary systems.
The general equilibrium relationship for VLE can be
expressed by the following equation.21
Figure 2. T−x−y phase equilibrium for the cyclohexanone (1) +
⎡ V L(p − ps ) ⎤ toluene (2) system at 101.3 kPa: ●, x, T experimental data; ○, y, T
exp⎢ i ⎥
i
̂ =
ϕiyp xiγϕ s s
p experimental data; ■, x, y, T literature data by Kireev et al.8; solid line,
i i i i
⎢⎣ RT ⎥⎦ (1) correlated results by the NRTL model; dashed line, correlated results
by the UNIQUAC model; dashed-dotted line, correlated results by the
where p and T are the total pressure and the temperature in the Wilson model. dotted line, predicted results by the UNIFAC model.
equilibrium system, respectively; psi is the saturated pressure of
pure component i; ϕ̂ i is the fugacity coefficient of component i C 2i
in the vapor phase; ϕsi is the fugacity coefficient at the saturated ln(pi s /kPa) = C1i + + C4iT + C5i ln T + C6iT C7i
T + C 3i
pressure; γi is the activity coefficient in the liquid phase; VLi is
the liquid molar volume; xi and yi are the liquid- and vapor- (3)
phase mole fractions of component i at equilibrium, over the temperature range C8i ≤ T < C9i. The Antoine
respectively; and R is the universal gas constant. parameters C1i to C9i for each component i were taken from the
At low pressure, the Poynting factor exp[VLi (p − psi )/RT] is Aspen property databank24 and are presented in Table 3. The
approximately equal to 1.22 Besides, the vapor phase can be calculated activity coefficients of component i (γi) are listed in
considered as an ideal gas, and the pressure dependence of the Table 2.
liquid-phase fugacity can be neglected. Therefore, eq 1 can be 3.2. Thermodynamic Consistency Tests. To verify the
simplified as quality of the data obtained, the thermodynamic consistency of
yp
i
= xiγipis (2) all of the experimental data was checked using the Herington,
Van Ness, infinite dilution, and pure-component consistency
The saturated pressure of pure component i can be tests following the strategy described by Kang et al.12,25
calculated using the extended Antoine equation:23 The Herington method9,26 is expressed as follows:
C DOI: 10.1021/acs.jced.6b00877
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

using the NRTL, UNIQUAC, or Wilson activity coefficient

model, and yiexptl is the experimental mole fraction of
component i in the vapor phase. In this test, the isobaric
VLE data could be considered as thermodynamically consistent
if Δy is not greater than 1. According to the results of
correlation, the values of Δy obtained using the NRTL,
UNIQUAC, and Wilson models are 0.225, 0.325, and 0.457 for
the cyclohexanone + benzene system; 0.167, 0.102, and 0.172
for the cyclohexanone + toluene system; and 0.122, 0.108, and
0.155 for the cyclohexanone + p-xylene system, respectively. All
the values of Δy are less than 1, indicating that all of the
measured VLE data pass the thermodynamic consistency test.
The infinite dilution test was used to check the consistency
of data in the dilute concentration region.11 The infinite
dilution test is defined in terms of the following functions:
GE /(x1x 2RT ) − ln(γ1/γ2)
I1 = 100
Figure 3. T−x−y phase equilibrium for the cyclohexanone (1) + p- ln(γ1/γ2)
xylene (2) system at 101.3 kPa: ●, x, T experimental data; ○, y, T x1= 0 (7)
experimental data; solid line, correlated results by the NRTL model;
dashed line, correlated results by the UNIQUAC model; dashed- GE /(x1x 2RT ) − ln(γ1/γ2)
dotted line, correlated results by the Wilson model. dotted line, I2 = 100
ln(γ1/γ2)
predicted results by the UNIFAC model. x2 = 0 (8)

1 In the infinite dilution test, I1 and I2 cannot be greater than 30.

S − S− |∫ ln(γ1/γ2) dx1| For the regression of GE/(x1x2RT) and ln(γ1/γ2), the extended
D = 100 × + = 100 × 01 Redlich−Kister equations (eqs 9 and 10)27 were used:
S+ + S− ∫0 |ln(γ1/γ2)| dx1 (4)
GE /RT = x1x 2[c1 + c 2(x1 − x 2) + c3(x1 − x 2)2 + ...]
Tmax − Tmin (9)
J = 150 ×
Tmin (5) ln(γ1/γ2) = d1 + d 2(x 2 − x1) + d3(6x1x 2 − 1)
where S+ and S− are the areas above and below the horizontal + d4(x 2 − x1)(1 − 8x1x 2) + ... (10)
coordinate axis on the plot of ln(γ1/γ2) versus x, respectively,
The values of I1 and I2 for the three systems are listed in Table
and Tmax and Tmin are the maximum and minimum boiling
4. All of the I1 and I2 values are less than 30, indicating that the
temperatures in the system, respectively. The criteria of
VLE data for the three systems pass the infinite dilution test.
consistency of the Herington test is that the value of |D − J|
is smaller than 10. The values of |D − J| for the cyclohexanone
+ benzene, cyclohexanone + toluene, and cyclohexanone + p- Table 4. Results of the Infinite Dilution Test
xylene systems at 101.3 kPa are 7.5034, 5.6244, and 8.9465, system I1 I2
respectively, indicating that the experimental data are cyclohexanone (1) + benzene (2) 27.48 25.51
thermodynamically consistent. cyclohexanone (1) + toluene (2) 22.30 9.74
The Van Ness test10 is defined as follows: cyclohexanone (1) + p-xylene (2) 16.81 28.33
N N
1 1
Δy = ∑ Δyi = ∑ 100|yicalcd − yiexptl | The pure-component consistency test12,28 was used to
N i=1
N i=1 (6)
analyze the consistency of the “end points” of the VLE data.
where N is the number of experimental data points, ycalcd
i is the In this test, ΔP10 and ΔP20 should be less than 1. ΔP01 and ΔP02
mole fraction of component i in the vapor phase calculated are expressed as follows:

Table 3. Parameters of the Extended Antoine Equationa

cyclohexanone benzene toluene p-xylene
C1i 78.5162 76.1992 70.0372 81.8122
C2i −7944.40 −6486.20 −6729.80 −7741.20
C3i 0.0 0.0 0.0 0.0
C4i 0.0 0.0 0.0 0.0
C5i −9.2862 −9.2194 −8.1790 −9.8693
C6i 4.9957·10−6 6.9844·10−6 5.3017·10−6 6.0770·10−6
C7i 2.00 2.00 2.00 2.00
C8i/K 242.00 278.68 178.18 286.41
C9i/K 653.00 562.05 591.75 616.20

a
Taken from the Aspen property databank.

D DOI: 10.1021/acs.jced.6b00877
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Pbubble(x1 → 1) − P10 Table 7. NRTL, UNIQUAC, and Wilson Equations Used in

ΔP10 = This Work
P10 (11)
NRTL
Pbubble(x1 → 0) − P20 ∑j xjτjiGji xjGij ⎛ ∑ x τ G ⎞
ΔP20 = ln γi = + ∑ ⎜⎜τij − m m mj mj ⎟⎟
P20 (12) ∑k xkGki j
∑k xkGkj ⎝ ∑k xkGkj ⎠

bij
where Pbubble is the bubble-point pressure of the mixture and P01 τij = aij + Gij = exp(− αijτij)
and P02 are the pure-component vapor pressures. The results of T
the pure-component consistency test of the VLE data are listed UNIQUAC
in Table 5. As can be seen from the results, all of the ΔP01 and ϕi Z θ ∑j θjtτij ϕ
ΔP02 values are less than 1, indicating that the VLE data for the ln γi = ln
xi
+
2
qi ln i − qit ln tit − qit
ϕi t jt
+ li + qit − i
xi
∑ xjlj
j
three systems pass the pure-component consistency test.
⎛ bij ⎞
τij = exp⎜aij + ⎟
Table 5. Results of the Pure-Component Consistency Test ⎝ T⎠
system ΔP01 ΔP02 Wilson
cyclohexanone (1) + benzene (2) 0.0000 0.0003 Aji xj
ln γi = 1 − ln(∑ Aijxj) − ∑
cyclohexanone (1) + toluene (2) 0.0000 0.0009 j j
∑k Ajk xk
cyclohexanone (1) + p-xylene (2) 0.0000 0.0003
bij
ln Aij = aij +
T

The overall quality factor, QVLE, was used to check the VLE
data for the three systems. QVLE is expressed as follows:25
FPure(FHerington + FVanNess + FInf.Dil.)
Q VLE =
0.25·3
The quality factors for the Herington, Van Ness, infinite
dilution, and pure-component consistency tests and the values
of QVLE are listed in Table 6. The quality factors for the pure-
component consistency test (FPure) are equal to 1, since the
vapor pressures agree within 0.01P0 for both components in the
three systems. The overall quality factors QVLE for the three
systems are equal to 1, indicating that the VLE data are
thermodynamically consistent.
3.3. Correlations and Predictions for the VLE Data. In
the present work, all of the VLE data for the cyclohexanone +
benzene, cyclohexanone + toluene, and cyclohexanone + p-
xylene systems were correlated using NRTL,13 UNIQUAC,14
and Wilson15 activity coefficient models. The corresponding
where N is the number of experimental data points; the
superscripts exptl and calcd denote experimental data and
calculated values, respectively; T, P, x, and y are the equilibrium
(13) temperature, pressure, and liquid- and vapor-phase mole
fractions, respectively; and σk is the standard deviation in
quantity k. The standard deviations for the temperature,
pressure, and liquid- and vapor-phase compositions are 0.1 K,
0.1 kPa, 0.001, and 0.001, respectively.
The root-mean-square deviations (RMSDs) and average
absolute deviations (AADs) of temperature and vapor-phase
mole fraction between the experimental and calculated values
for the three activity coefficient models were calculated:
⎡N ⎤1/2
⎢
RMSD = ∑ (Xi calcd
− Xi ) / N ⎥
exptl 2
⎢⎣ i = 1 ⎥⎦
N

equations are presented in Table 7. As recommended by Renon AAD = ∑ |Xicalcd − Xiexptl|/N

and Prausnitz,13 the nonrandomness parameter (αij) in the i=1
NRTL model was set at 0.3. In the regression calculation where X = T or y1. The regressed binary interaction parameters
performed by Aspen Plus, minimization of the maximum- for the NRTL, UNIQUAC, and Wilson models and the RMSD
likelihood objective function was used to obtain the interaction and AAD values for each system are listed in Table 8. From the
parameters of the models. The maximum-likelihood objective RMSD and AAD values in Table 8, it can be seen that the
function is expressed as RMSDs for T and y1 are less than 0.12 K and 0.0058,
⎡⎛ exptl ⎛ pexptl − pcalcd ⎞2 respectively, and the AADs for T and y1 are less than 0.10 K
− Ticalcd ⎞
N 2
⎢⎜ Ti and 0.0046, respectively. The results show that all of the models
⎟ + ⎜⎜
⎟ ⎟
i i
Q = ∑ ⎢⎜ ⎟ can correlate the VLE data for the cyclohexanone + benzene,
i = 1 ⎣⎝ σT ⎠ ⎝ σp ⎠
cyclohexanone + toluene, and cyclohexanone + p-xylene binary
⎛ x exptl − x calcd ⎞2 ⎛ y exptl − y calcd ⎞ ⎤
2 systems at 101.3 kPa with reasonable deviations.
+ ⎜⎜ i i
⎟⎟ + ⎜⎜ i i ⎟⎥ Meanwhile, the UNIFAC group contribution model16 was
⎟⎥ used to predict the VLE data for the three systems. The group
⎝ σx ⎠ ⎝ σy ⎠⎦ (14) types and group numbers for the compounds are shown in

Table 6. Quality Factors for the Thermodynamic Consistency Tests

system FHerington FVanNess FInf.Dil. FPure QVLE

cyclohexanone (1) + benzene (2) 0.25 0.25 0.25 1.00 1.00
cyclohexanone (1) + toluene (2) 0.25 0.25 0.25 1.00 1.00
cyclohexanone (1) + p-xylene (2) 0.25 0.25 0.25 1.00 1.00

E DOI: 10.1021/acs.jced.6b00877
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 8. Binary Interaction Parameters, Root-Mean-Square Deviations (RMSDs), and Average Absolute Deviations (AADs) for
the Equilibrium Temperature (T) and Vapor-Phase Mole Fraction (y1) for the Activity Coefficient Models
binary interaction parameters RMSDs AADs
model aij aji bij/K bji/K α T/K y1 T/K y1
Cyclohexanone (1) + Benzene (2)
NRTL −2.031 10.656 233.188 −2944.122 0.3 0.08 0.0032 0.07 0.0023
UNIQUAC 2.345 −9.352 −562.983 2867.543 0.10 0.0042 0.09 0.0032
Wilson −30.797 2.745 10291.077 −649.634 0.12 0.0058 0.10 0.0046
UNIFAC 0.13 0.0054 0.10 0.0041
Cyclohexanone (1) + Toluene (2)
NRTL 0.919 0 −878.076 1034.641 0.3 0.08 0.0021 0.07 0.0017
UNIQUAC 0.523 −1.981 96.579 222.397 0.05 0.0014 0.04 0.0010
Wilson −13.147 1.258 4228.609 −143.773 0.08 0.0027 0.07 0.0017
UNIFAC 0.06 0.0013 0.04 0.0010
Cyclohexanone (1) + p-Xylene (2)
NRTL 0.328 5.036 −585.237 −1227.862 0.3 0.04 0.0015 0.03 0.0012
UNIQUAC 1.394 −5.017 −301.544 1606.207 0.04 0.0013 0.03 0.0011
Wilson −28.000 3.790 10857.376 −1263.649 0.04 0.0020 0.04 0.0016
UNIFAC 0.05 0.0013 0.04 0.0011

Table 9. The volume parameters (Rk) and area parameters (Qk) consistency. The VLE data for the three binary systems were
are listed in Table 10.29 All of the UNIFAC-predicted results correlated using the NRTL, UNIQUAC, and Wilson activity
coefficient models, and the binary interaction parameters were
Table 9. Group Type and Group Number for Each regressed. All of the results calculated using the NRTL,
Component UNIQUAC, and Wilson models showed good agreement with
the experimental data. The UNIFAC model was also used to
compound group type group number
predict the VLE data and gave good prediction results.
cyclohexanone CH2CO 1 Furthermore, the determined vapor−liquid equilibrium data
CH2 4 and the regressed binary interaction parameters will be helpful
benzene ACH 6 for the separation process.

■
toluene ACH 5
ACCH3 1 ASSOCIATED CONTENT
p-xylene ACH 4
*
S Supporting Information
ACCH3 2
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jced.6b00877.
Table 10. Volume Parameters (Rk) and Area Parameters Comparisons for the cyclohexanone + benzene and
(Qk) of the Groupsa cyclohexanone + p-xylene systems under different
conditions (PDF)

■
main group Rk Qk
CH2CO 1.4457 1.1800 AUTHOR INFORMATION
CH2 0.6744 0.5400
Corresponding Author
ACH 0.5313 0.4000
*E-mail: xudongmei.cn@163.com. Telephone: +86 532 8605
ACCH3 1.2663 0.9680
a
7798.
Taken from Magnussen et al.29
ORCID
Jun Gao: 0000-0003-1145-9565
for the three systems are listed in Table 2, and the RMSDs and Dongmei Xu: 0000-0002-5770-0513
AADs of the temperature and vapor-phase mole fraction Funding
between the experimental and the predicted values for the three The authors thank the National Natural Science Foundation of
systems are reported in Table 8. The comparisons between the China (Grant 21306093) for financial support of this work.
experimental and predicted values are plotted in Figures 1 to 3,
which show good agreements. The UNIFAC model could give Notes
The authors declare no competing financial interest.

■
good predictions for the three systems.

4. CONCLUSIONS
The isobaric VLE data for the binary systems cyclohexanone +
benzene, cyclohexanone + toluene, and cyclohexanone + p-
xylene were determined at 101.3 kPa with a modified Rose-type
recirculating still. No azeotropic behavior was found in the
three binary systems. The experimental data were checked with
the Herington, Van Ness, infinite dilution, and pure-component
consistency tests, which showed good thermodynamic
REFERENCES
(1) Ritz, J.; Fuchs, H.; Kieczka, H.; Moran, W. C. In Ullmann’s
Encyclopedia of Industrial Chemistry; Wiley-VCH: Weinheim, Germany,
1986.
(2) Lorenzo, D.; Simon, E.; Santos, A.; Romero, A. Kinetic Model of
Catalytic Self-Condensation of Cyclohexanone over Amberlyst 15. Ind.
Eng. Chem. Res. 2014, 53 (49), 19117−19127.
(3) Bomhard, E. M.; Brendler-Schwaab, S. Y.; Freyberger, A.;
Herbold, B. A.; Leser, M.; Richter, K. H. o-Phenylphenol and its

F DOI: 10.1021/acs.jced.6b00877
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

sodium and potassium salts: a toxicological assessment. Crit. Rev. (25) Martins, V. D.; Granato, M. A.; Rodrigues, A. E. Isobaric
Toxicol. 2002, 32, 551−625. Vapor−Liquid Equilibrium for Binary Systems of 2,2,4-Trimethylpen-
(4) Chen, Y.; Yuan, S.; Yin, H.; Chen, Z.; Mao, C. Kinetics of the tane with o-Xylene, m-Xylene, p-Xylene, and Ethylbenzene at 250 kPa.
reversible dimerization reaction of cyclohexanone over γ-alumina J. Chem. Eng. Data 2014, 59, 1499−1506.
catalyst. React. Kinet., Mech. Catal. 2011, 102, 183−194. (26) Wisniak, J. A new test for the thermodynamic consistency of
(5) Lorenzo, D.; Santos, A.; Simon, E.; Romero, A. Kinetic of Alkali vapor−liquid equilibrium. Ind. Eng. Chem. Res. 1993, 32 (7), 1531−
Catalyzed Self-Condensation of Cyclohexanone. Ind. Eng. Chem. Res. 1533.
2013, 52, 2257−2265. (27) Chao, K. C. Isobaric vapor−liquid equilibria. Ind. Eng. Chem.
(6) Matteoli, E.; Lepori, L. Isothermal Liquid-Vapor Equilibria of 1959, 51, 93−94.
Mixtures Containing Organic Compounds. 2. Excess Gibbs Free (28) Frenkel, M.; Chirico, R. D.; Diky, V.; Yan, X.; Dong, Q.; Muzny,
Energies of a Hydrocarbon or Tetrachloromethane + a Cyclic Ketone C. ThermoData Engine (TDE): Software Implementation of Dynamic
at 298.15 K. J. Chem. Eng. Data 1988, 33, 247−250. Data Evaluation Concept. J. Chem. Inf. Model. 2005, 45, 816−838.
(7) Comelli, F.; Francesconi, R. Isobaric Vapor−Liquid Equilibrium (29) Magnussen, T.; Rasmussen, P.; Fredenslund, A. UNIFAC
in Binary Mixtures of m- and p-Xylenes with Cyclohexene and parameter table for prediction of liquid−liquid equilibria. Ind. Eng.
Cyclohexanone. Can. J. Chem. Eng. 1985, 63, 344−347. Chem. Process Des. Dev. 1981, 20, 331−339.
(8) Kireev, V. A.; Sheinker, Yu. N.; Peresleni, E. M. hase equilibrium
of liquid-vapor in several binary systems. Zh. Fiz. Khim. 1952, 26,
352−7.
(9) Herington, E. F. G. Tests for the Consistency of Experimental
Isobaric Vapor−Liquid Equilibrium Data. J. Inst. Pet. 1951, 37, 457−
470.
(10) Van Ness, H. C.; Byer, S. M.; Gibbs, R. E. Vapor−Liquid
equilibrium: Part I. An appraisal of data reduction methods. AIChE J.
1973, 19, 238−244.
(11) Kojima, K.; Moon, H. M.; Ochi, K. Thermodynamic
Consistency Test of Vapor−Liquid Equilibrium Data. Fluid Phase
Equilib. 1990, 56, 269−284.
(12) Kang, J. W.; Diky, V.; Chirico, R. D.; Magee, J. W.; Muzny, C.
D.; Abdulagatov, I.; Kazakov, A. F.; Frenkel, M. Quality Assessment
Algorithm for Vapor−Liquid Equilibrium Data. J. Chem. Eng. Data
2010, 55, 3631−3640.
(13) Renon, H.; Prausnitz, J. M. Local Compositions in
Thermodynamic Excess Functions for Liquid Mixtures. AIChE J.
1968, 14, 135−144.
(14) Abrams, D. S.; Prausnitz, J. M. Statistical Thermodynamics of
Liquid Mixtures: A New Expression for the Excess Gibbs Energy of
Partly or Completely Miscible Systems. AIChE J. 1975, 21, 116−128.
(15) Wilson, G. M. Vapor−Liquid Equilibrium. XI. A New
Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc.
1964, 86, 127−130.
(16) Fredenslund, A.; Jones, R. L.; Prausnitz, J. M. Group-
contribution estimation of activity coefficients in nonideal liquid
mixtures. AIChE J. 1975, 21, 1086−1099.
(17) Huang, X. J.; Xia, S. Q.; Ma, P. S.; Song, S.; Ma, B. J. Vapor−
Liquid Equilibrium of N-Formylmorpholine with Toluene and Xylene
at 101.33 kPa. J. Chem. Eng. Data 2008, 53, 252−255.
(18) Zhu, Z. Y.; Ma, Y. X.; Gao, J. Isobaric Vapor−Liquid Equilibria
for Binary Systems of Acetic Acid + Benzene, Chloroacetic Acid +
Benzene, and Dichloroacetic Acid + Benzene at 101.33 kPa. J. Chem.
Eng. Data 2010, 55, 3387−3390.
(19) Zhang, L. Z.; Gao, Y. C.; Xu, D. M.; Zhang, Z. S.; Gao, J.; Pratik,
D. Isobaric Vapor−Liquid Equilibrium for Binary Systems of Allyl
Alcohol with Water, Methanol, and Ethanol at 101.3 kPa. J. Chem. Eng.
Data 2016, 61 (6), 2071−2077.
(20) Gao, J.; Li, H.; Xu, D. M.; Zhang, L. Z.; Zhao, L. W.; Li, C. L.
Isobaric Vapor−Liquid Equilibrium for Binary Systems of Thioglycolic
Acid with Water, Butyl Acetate, Butyl Formate, and Isobutyl Acetate at
101.3 kPa. J. Chem. Eng. Data 2017, 62 (1), 355−361.
(21) Smith, J. M.; Van Ness, H. C.; Abbott, M. M. Introduction to
Chemical Engineering Thermodynamics, 6th ed.; McGraw-Hill: New
York, 2001.
(22) Gao, J.; Zhao, L. W.; Zhang, L. Z.; Xu, D. M.; Zhang, Z. S.
Isobaric Vapor−Liquid Equilibrium for Binary Systems of 2,2,3,3-
Tetrafluoro-1-propanol + 2,2,3,3,4,4,5,5-Octafluoro-1-pentanol at 53.3,
66.7, 80.0 kPa. J. Chem. Eng. Data 2016, 61, 3371−3376.
(23) O’Connell, J. P.; Prausnitz, J. M.; Poling, B. E. The Properties of
Gases and Liquids, 4th ed.; McGraw-Hill: New York, 1987.
(24) Aspen Plus software, version 7.2; Aspen Technology, Inc.:
Burlington, MA, 2001.

G DOI: 10.1021/acs.jced.6b00877
J. Chem. Eng. Data XXXX, XXX, XXX−XXX