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org/jced Article

Isobaric Vapor−Liquid Equilibria of Binary Mixtures of

γ‑Valerolactone + Acetone and Ethyl Acetate
Dav́ id Havasi, Dań iel Farkas, and Laś zló T. Mika*
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sı Supporting Information

ABSTRACT: γ-Valerolactone (GVL) has recently been considered as a suitable solvent for
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synthesis and catalysis. By the application of GVL in scaled-up processes, it can be mixed with
various components, including commonly utilized polar aprotic solvents such as acetone and
ethyl acetate. Herein, isobaric vapor−liquid equilibria (VLE) of acetone, ethyl acetate, and γ-
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valerolactone were investigated at p = 101.3 kPa with a vapor−liquid equilibrium. In addition,

the VLE data series of GVL−water binary mixture was extended. The experimental data were
correlated with Wilson, NRTL, and UNIQUAC activity coefficient models, whereas the
results showed a greater difference to the UNIFAC model calculations. The refractive indexes
of the mixture were also determined in the whole concentration range at T = 293.2 and 298.2
K.

■ INTRODUCTION
In the past decade, many efforts have been addressed to the
identification and characterization of novel renewable-based
Scheme 1. γ-Valerolactone
platform chemicals, which could either replace the currently
used fossil-based building blocks of chemical industry or serve
as the renewable feedstocks for their production.1,2 Among
these chemicals, γ-valerolactone (GVL, IUPAC name: 5-
methyldihydrofuran-2(3H)-one; Scheme 1), which was first
proposed as a sustainable liquid by Horváth and co-workers,3
has recently received significant interest and therefore several
innovative applications were demonstrated for its utilization.
GVL can easily be obtained from biomass via levulinic acid4
and can be used for the production of alkanes and alkenes,4
transportation fuels,5 ionic liquids,6,7 monomers for the
polymer industry,8 etc., just to name a few. The application
of GVL as an environmentally benign, aprotic, and dipolar
solvent for the synthesis and catalysis has also received
significant interest recently.9−16
While the chemistry of GVL has widely been studied, several
fundamental engineering data have to be determined and
considered concerning its production, purification, and
utilization. It was earlier shown that GVL does not form a
measurable amount of peroxide under air17 and does not make
an azeotropic mixture with water,18 C1−C3 alcohols19 and
formic acid.20 Its temperature-dependent vapor pressure as a
key property even in the case of solvent utilization was recently
measured by several groups.18,21−23 Pokki and co-workers
determined the isobaric vapor−liquid equilibrium (VLE) data
of the GVL−furfural system23 and investigated the GVL−
water binary mixture including its isothermal VLE data, the
excess enthalpy, and density of aqueous GVL solutions.22
Růzǐ čka measured the enthalpy of vaporization and fusion as
well as condensed phase heat capacity of GVL.21 Ř ehák
studied the binary liquid−liquid equilibria of GVL with
selected hydrocarbons referring to its biofuel applications24
and determined its thermal and volumetric properties.25
Ceriani’s group reported liquid−liquid equilibria data for
three n-tetradecane-based ternary mixtures of GVL.26 How-
ever, for its solvent or solvent−component application, the
separation issues of GVL from well-known and commonly
utilized organic reaction media is crucial and therefore its
investigation is highly desired.
Herein, we report the vapor−liquid equilibrium (VLE) data
of three GVL-containing binary mixtures, i.e., water−GVL,
acetone−GVL, and ethyl acetate−GVL systems at 101.3 kPa.
The Wilson, NRTL, and UNIQUAC binary interaction
parameters (BIPs) were determined, as well.
Received: April 30, 2019
Accepted: January 14, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jced.9b00379

A J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. CAS Registry Number, Mass Fraction Purity, and Refractive Indexes (nD) of the Chemicals
nD at 293.2 K
CAS reg. purification mass this analysis
component no. suppliers method fraction worka literature method(s)b
water 7732-18-5 Sigma-Aldrich none ≥0.999 1.3330 1.333027 Rf.
acetone (propan-2-one) 67-64-1 Molar distillation ≥0.999 1.3588 1.358628 Rf./GC−MSa
Chemicals
ethyl acetate (ethyl ethanoate) 141-78-6 Merck distillation ≥0.999 1.3723 1.372529 Rf./GC−MSa
γ-valerolactone (4,5-dihydro-5-methyl-2(3H)- 108-29-2 Sigma-Aldrich distillation ≥0.999 1.4339 1.433918 Rf./GC−MSa
furanone)
a
Standard uncertainty u(nD) = 0.0001. bGas chromatography−mass spectrometry (GC−MS): gas chromatograph equipped with MS detector, Rf.:
refractometry.

Table 2. Antoine Constants of Chemicals Used for this good agreement with the literature data. Chemicals except
Worka water were purified by vacuum distillation. Constants of the
Antoine constant (kPa, ethyl Antoine eq 1 of the applied chemicals are presented in Table 2.
K) water acetone acetate For calculating the activity coefficients of GVL, a Cox eq 2
A 7.11564 6.42448 7.0337 fitted by Růzǐ čka21 was used with the following parameters: A0
B 1687.537 1312.253 1869.43 = 2.847077, A1 = −1.324751 × 10−3, A2 = 1.060314 × 10−6, T0
C −42.98 −32.445 22.19
= 478.00 K, and p0 = 99 795 Pa.
temp. range (K) 273.20−473.20 259.16−507.60 292−467
a
Water: ref 30, acetone: ref 31, ethyl acetate: ref 32. B
log(p) = A −

■ EXPERIMENTAL SECTION
i Ty n
(T + C ) (1)

= jjj1 − 0 zzze(∑i=0 A i(T ) )

Chemicals. The CAS registry numbers, mass fraction
p0 k T{
p i
purity, and refractive indexes of the chemicals used are ln
presented in Table 1. The experimental refractive indexes show (2)

Table 3. VLE Data (T, Temperature; x, Liquid Mole Fraction; y, Vapor Mole Fraction) of Water−GVL at p = 101.3 kPaa
experimental UNIQUAC
T (K) x1 y1 γ1 γ2 T (K) y1
373.2 1.0000 1.0000 1.0000 373.1 1.0000
373.3 0.9867 0.9936 1.0061 15.4655 373.3 0.9943
373.4 0.9701 0.9884 1.0144 12.3815 373.5 0.9899
373.5 0.9548 0.9867 1.0252 9.3295 373.7 0.9874
373.6 0.9415 0.9851 1.0343 8.0400 373.8 0.9860
373.7 0.9182 0.9846 1.0563 5.9116 373.9 0.9846
373.6 0.8990 0.9832 1.0810 5.2603 374.0 0.9840
373.7 0.8690 0.9826 1.1138 4.1719 374.1 0.9835
373.8 0.8336 0.9823 1.1567 3.3177 374.1 0.9832
373.9 0.8039 0.9811 1.1936 3.0053 374.2 0.9831
374.0 0.7677 0.9807 1.2451 2.5692 374.3 0.9828
374.2 0.7321 0.9804 1.2960 2.2453 374.4 0.9825
374.3 0.7002 0.9801 1.3497 2.0309 374.5 0.9821
374.4 0.6770 0.9799 1.3909 1.8949 374.7 0.9817
374.6 0.6531 0.9789 1.4277 1.8303 374.9 0.9813
374.8 0.6296 0.9787 1.4728 1.7190 375.1 0.9808
375.1 0.6054 0.9785 1.5153 1.6076 375.4 0.9802
375.2 0.5972 0.9785 1.5279 1.5695 375.6 0.9800
375.5 0.5778 0.9781 1.5619 1.5055 375.9 0.9795
375.8 0.5665 0.9779 1.5762 1.4561 376.0 0.9791
376.4 0.5356 0.9773 1.6343 1.3674 376.6 0.9780
377.0 0.5069 0.9769 1.6871 1.2748 377.3 0.9769
378.1 0.4748 0.9761 1.7324 1.1787 378.1 0.9752
378.8 0.4487 0.9753 1.7883 1.1271 378.9 0.9738
379.8 0.4257 0.9739 1.8183 1.0978 379.7 0.9723
381.4 0.3937 0.9729 1.8600 1.0088 381.0 0.9699
average absolute deviation (AAD)b 0.3 0.0013

a
Standard uncertainities u are u(T) = 0.1 K; u(P) = 0.3 kPa; u(x1) = u(y1) = 0.0005. bAAD of T = (1/N)∑Ni |ΔTi| where ΔTi = Ti,calc − Ti,exp; AAD
of y = (1/N)∑Ni |Δyi| where Δyi = yi,calc − yi,exp, N = number of data points.

B https://dx.doi.org/10.1021/acs.jced.9b00379
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Apparatus and Procedure. The vapor−liquid equilibrium
measurements were performed on a modified Gillespie still,
which was shown in detail in ref 19. The temperature was
measured with a digital thermometer (223−573 K) with an
accuracy of 0.1 K. The uncertainty in pressure was 0.3 kPa
during the experiments.
Sample Analysis. GC−MS measurements of selected
samples were performed on a Shimadzu GCMS-QP2010 SE
mass spectrometer equipped with an SGE BP5 column (0.22
mm × 0.33 mm × 0.25 μm, length: 25 m). The GC analysis of
selected samples was performed on an HP 6890N instrument
equipped with a flame ionization detector (FID) with an HP
INNOWvax capillary column (15 m × 0.25 μm × 0.25 μm)
using H2 as a carrier gas and operating in splitless mode.
Toluene was used as an internal standard. For the analysis of
refractive indexes, a Carl Zeiss Abbe refractometer (Type G)
was applied. The accuracy of the applied refractometer is
0.0001 at 293.2 and 298.2 K according to the manufacturer.
For analyzing the equilibrium samples, their refractive indexes
were determined in the whole concentration range at T =
273.2 and 278.2 K. In addition, GC−MS analysis was
performed for certain equilibrium and calibration samples as
a validation for the refractometric method.
in the Supporting Information. The activity coefficients
presented were calculated by eq 3.
yp
γi = i 0
xipi (3)
First, we extended our previously determined VLE data of
water−GVL binary mixture using our modified Gillespie still.19
Using the extended data series (Table 3 and Figure 1), new
binary interaction parameters for the UNIQUAC model were
regressed giving ΔUij = −89.70 cal/gmol and ΔUji = 375.41
cal/gmol. As the extended data covers a wider concentration
range, the new parameters show a better fit below 0.5 x1
concentration than the parameters in ref 18.
The isobaric vapor−liquid equilibrium of acetone−GVL and
ethyl acetate−GVL was measured at p = 101.3 kPa. With the
experimental data, Wilson, NRTL, and UNIQAC parameters
were regressed and the results were compared with the

■ RESULTS AND DISCUSSION

The refractive indexes were determined in the whole
concentration range for acetone−GVL and ethyl acetate−

Figure 2. T−x−y plot of acetone−GVL binary mixture at p = 101.3

kPa. (Filled circle) Liquid composition points, (circle) vapor
composition points, (solid line) UNIQUAC model, (dashed line)
NRTL model, (dotted line) Wilson model, (red dash line) Raoult’s
law calculations, and (red hyphen) UNIFAC model calculation.

Figure 1. T−x−y plot of water−GVL binary mixture at p = 101.3 kPa.

(Filled circle) This work, (circle) previously measured data points
from ref 18, (solid line) UNIQUAC model (this work), and (dashed
line) UNIQUAC model (from ref 18).

GVL systems at T = 293.2 and 298.5 K. The data are presented

in Tables S1 and S2 (Supporting Information). The
concentration vs refractive index plots are depicted in Figures
S1 and S2 (Supporting Information). The data were correlated
by fourth-order polynomial equations (S1 and S2, Supporting
Information) for acetone−GVL and ethyl acetate−GVL
mixtures with R2 > 0.9999 for all cases.
Using the experimentally gathered data, Wilson,33 NRTL,34 Figure 3. T−x−y plot of ethyl acetate−GVL binary mixture at p =
and UNIQAC35 binary interaction parameters (BIPs) were 101.3 kPa. (Filled circle) Liquid composition points, (circle) vapor
regressed and the results were compared with Raoult’s law and composition points, (solid line) UNIQUAC model, (dashed line)
UNIFAC36 model calculations. The applied structural NRTL model, (dotted line) Wilson model, (red dashed line) Raoult’s
parameters for UNIQUAC and UNIFAC models are presented law calculations, and (red hyphen) UNIFAC model calculation.

C https://dx.doi.org/10.1021/acs.jced.9b00379
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Table 4. VLE Data (T, Temperature; x, Liquid Mole Fraction; y, Vapor Mole Fraction) of Acetone−GVL at p = 101.3 kPaa
calculated data
experimental data Wilson NRTL UNIQUAC
T (K) x1 y1 γ1 γ2 T (K) y1 T (K) y1 T (K) y1
329.4 1.0000 1.0000 1.0000 329.3 1.0000 329.3 1.0000 329.3 1.0000
329.5 0.9957 0.9996 1.0040 24.0096 329.4 0.9999 329.4 0.9999 329.4 0.9999
329.6 0.9921 0.9994 1.0040 19.9900 329.5 0.9999 329.5 0.9999 329.5 0.9999
329.8 0.9852 0.9992 1.0040 14.4166 329.7 0.9999 329.8 0.9999 329.7 0.9999
330.2 0.9715 0.9990 1.0040 9.8645 330.2 0.9999 330.2 0.9998 330.2 0.9999
330.5 0.9613 0.9990 1.0043 7.3335 330.5 0.9999 330.5 0.9998 330.5 0.9999
330.8 0.9514 0.9989 1.0044 6.0511 330.8 0.9998 330.8 0.9997 330.8 0.9998
331.0 0.9448 0.9989 1.0045 5.4060 331.0 0.9998 331.0 0.9996 331.0 0.9998
331.2 0.9367 0.9988 1.0047 4.8784 331.2 0.9997 331.2 0.9995 331.2 0.9997
331.4 0.9317 0.9988 1.0049 4.5932 331.4 0.9997 331.4 0.9995 331.4 0.9997
331.7 0.9206 0.9987 1.0050 4.0534 331.7 0.9996 331.7 0.9994 331.7 0.9996
332.0 0.9128 0.9987 1.0051 3.8017 331.9 0.9996 332.0 0.9994 332.0 0.9996
332.4 0.9003 0.9986 1.0053 3.3916 332.3 0.9995 332.4 0.9992 332.3 0.9995
332.8 0.8880 0.9986 1.0056 3.0709 332.7 0.9994 332.8 0.9992 332.7 0.9995
333.0 0.8802 0.9985 1.0059 2.9731 333.0 0.9994 333.1 0.9991 333.0 0.9994
333.7 0.8611 0.9984 1.0061 2.6012 333.6 0.9992 333.7 0.9989 333.6 0.9993
334.0 0.8524 0.9984 1.0063 2.5009 333.9 0.9992 334.0 0.9989 333.9 0.9993
334.5 0.8381 0.9983 1.0065 2.3122 334.4 0.9991 334.5 0.9987 334.4 0.9991
335.1 0.8214 0.9982 1.0067 2.1610 335.0 0.9990 335.1 0.9985 335.0 0.9990
335.4 0.8116 0.9981 1.0070 2.1028 335.3 0.9989 335.5 0.9984 335.3 0.9990
336.0 0.7968 0.9979 1.0072 2.0304 335.8 0.9987 336.0 0.9981 335.9 0.9988
336.4 0.7861 0.9978 1.0075 1.9908 336.2 0.9987 336.4 0.9980 336.2 0.9987
337.7 0.7516 0.9974 1.0080 1.9238 337.5 0.9984 337.8 0.9976 337.5 0.9985
339.3 0.7124 0.9967 1.0109 1.8897 339.0 0.9979 339.3 0.9969 339.1 0.9980
339.9 0.6964 0.9965 1.0127 1.8636 339.7 0.9978 339.9 0.9967 339.8 0.9979
341.2 0.6651 0.9959 1.0183 1.8611 341.0 0.9975 341.2 0.9961 341.1 0.9976
342.7 0.6270 0.9950 1.0277 1.8557 342.7 0.9969 342.8 0.9953 342.9 0.9970
343.5 0.6065 0.9946 1.0356 1.8334 343.6 0.9966 343.7 0.9949 343.9 0.9967
344.3 0.5910 0.9941 1.0379 1.8259 344.4 0.9963 344.4 0.9945 344.7 0.9963
344.8 0.5778 0.9938 1.0433 1.8192 345.0 0.9961 344.9 0.9943 345.3 0.9961
average absolute deviation (AAD)b 0.1 0.0010 0.1 0.0005 0.1 0.0010
a
Standard uncertainties u are u(T) = 0.1 K; u(P) = 0.3 kPa; u(x1) = u(y1) = 0.0007. bAAD: see caption of Table 3.

UNIFAC model. The experimental and calculated data are N N

presented in Tables 4 and 5 and Figures 2 and 3. OF = ∑ (yexp,i − ycal,i )2 + ∑ (Texp,i − Tcal,i)2
It was revealed that no azeotropic mixtures were formed i=1 i=1 (4)
from the mixtures of GVL and acetone and GVL ethyl acetate d
in the investigated concentration range and pressure. The two b[1 + (1 − T / c) ]
mixtures show a positive deviation from Raoult’s law. By both V L /m 3 kmol−1 =
a (5)
mixtures, the UNIFAC calculations show a negative deviation
to the experimental data, based on the Txy data. yi
Ki =
In neither case could the whole concentration range be xi (6)
investigated due to the higher relative volatilities of the binary
mixtures. As the x1 concentration decreases, a smaller change K1
in the composition would result in larger temperature changes; α=
K2 (7)
therefore, even small condensate drops move the equilibrium
and no stable operation could be reached. The regressed data were compared with the experimental
Correlation of VLE System. Wilson, NRTL (with three results based on average absolute deviations (AAD) and
parameters), and UNIQUAC activity coefficient models were relative volatilities α (eq 7). Based on the AADs, the activity
applied to correlate the VLE data and determine the binary coefficient models show a good fit. The comparison of relative
interaction parameters for the corresponding mixtures by the volatilities was also performed for each data set including 10%
use of ChemCAD Chemical Process Simulation Software.37 error bars for the experimental data. The plots of relative
The minimization of ChemCAD’s objective function (eq 4) volatilities are presented in the Supporting Information
was utilized to obtain model parameters. Because Wilson molar (Figures S3−S5). In the case of water−GVL, the UNIQUAC
volumes are no longer used by ChemCAD, the estimation of model shows a good fit. In the case of acetone−GVL, the
liquid molar volumes is performed according to eq 5 (T/K). UNIQUAC and Wilson models show significant differences,
The parameters are presented in Tables 6 and 7 which are while the NRTL model represents a better fit between 0.55
from ChemCAD database.37 and 0.8 for x1. It should be noted however that this model
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Table 5. VLE Data (T, Temperature; x, Liquid Mole Fraction; y, Vapor Mole Fraction) of Ethyl Acetate−GVL at p = 101.3
kPaa
calculated data
experimental data Wilson NRTL UNIQUAC
T (K) x1 y1 γ1 γ2 T (K) y1 T (K) y1 T (K) y1
350.3 1.0000 1.0000 1.0000 350.4 1.0000 350.4 1.0000 350.4 1.0000
350.4 0.9951 0.9988 1.0037 22.3403 350.5 0.9999 350.5 0.9999 350.5 0.9999
350.5 0.9912 0.9985 1.0042 16.1647 350.6 0.9999 350.6 0.9999 350.6 0.9999
350.6 0.9877 0.9982 1.0044 13.2534 350.7 0.9998 350.7 0.9998 350.7 0.9998
350.7 0.9844 0.9982 1.0046 10.4242 350.8 0.9997 350.8 0.9997 350.8 0.9997
350.8 0.9800 0.9979 1.0057 9.5450 351.0 0.9997 351.0 0.9997 351.0 0.9997
350.9 0.9749 0.9977 1.0061 8.3640 351.1 0.9996 351.1 0.9996 351.1 0.9996
351.2 0.9664 0.9972 1.0066 7.4083 351.4 0.9994 351.4 0.9994 351.4 0.9994
351.5 0.9565 0.9967 1.0072 6.5683 351.7 0.9992 351.7 0.9992 351.7 0.9992
352.2 0.9334 0.9955 1.0089 5.7330 352.4 0.9989 352.4 0.9989 352.3 0.9988
352.6 0.9209 0.9950 1.0097 5.2179 352.8 0.9986 352.8 0.9986 352.7 0.9986
353.2 0.9022 0.9940 1.0108 4.9386 353.4 0.9983 353.4 0.9982 353.3 0.9983
353.8 0.8838 0.9930 1.0121 4.6929 353.9 0.9979 354.0 0.9979 353.8 0.9979
354.2 0.8663 0.9926 1.0180 4.2538 354.5 0.9976 354.5 0.9976 354.4 0.9976
354.8 0.8469 0.9916 1.0216 4.0570 355.1 0.9971 355.2 0.9971 355.0 0.9972
355.5 0.8243 0.9907 1.0267 3.7954 355.9 0.9966 355.9 0.9966 355.7 0.9967
356.1 0.8030 0.9903 1.0346 3.4518 356.6 0.9962 356.7 0.9962 356.4 0.9963
356.7 0.7846 0.9898 1.0410 3.2200 357.2 0.9957 357.3 0.9957 357.0 0.9959
357.2 0.7707 0.9893 1.0435 3.0868 357.7 0.9954 357.8 0.9953 357.4 0.9956
357.7 0.7567 0.9891 1.0468 2.9020 358.2 0.9950 358.3 0.9949 357.9 0.9953
358.4 0.7380 0.9884 1.0505 2.7718 358.9 0.9945 359.0 0.9944 358.6 0.9948
359.1 0.7176 0.9875 1.0572 2.6858 359.7 0.9940 359.8 0.9939 359.3 0.9943
360.2 0.6874 0.9865 1.0657 2.4682 360.8 0.9930 360.9 0.9929 360.4 0.9934
361.6 0.6425 0.9856 1.0948 2.1647 362.7 0.9915 362.8 0.9913 362.2 0.9920
365.3 0.5708 0.9823 1.1036 1.8621 365.9 0.9886 366.0 0.9883 365.4 0.9892
367.2 0.5306 0.9809 1.1230 1.6849 367.8 0.9866 367.9 0.9863 367.4 0.9873
369.8 0.4810 0.9781 1.1461 1.5519 370.5 0.9836 370.6 0.9834 370.2 0.9843
371.6 0.4541 0.9767 1.1529 1.4497 372.1 0.9817 372.2 0.9815 371.9 0.9824
372.7 0.4395 0.9758 1.1561 1.4025 373.1 0.9806 373.1 0.9804 372.8 0.9813
373.9 0.4232 0.9749 1.1590 1.3404 374.1 0.9792 374.1 0.9790 373.9 0.9799
374.7 0.4119 0.9744 1.1660 1.2963 374.9 0.9782 374.9 0.9780 374.7 0.9789
376.2 0.3915 0.9730 1.1744 1.2364 376.4 0.9761 376.3 0.9760 376.2 0.9768
378.7 0.3625 0.9697 1.1816 1.1904 378.6 0.9728 378.5 0.9727 378.6 0.9733
379.3 0.3505 0.9692 1.2018 1.1570 379.6 0.9712 379.4 0.9711 379.6 0.9717
381.2 0.3272 0.9678 1.2242 1.0811 381.6 0.9677 381.4 0.9678 381.7 0.9681
383.1 0.3060 0.9664 1.2415 1.0096 383.7 0.9641 383.4 0.9643 383.9 0.9644
average absolute deviation (AAD)b 0.4 0.0039 0.4 0.0038 0.2 0.0042
a
Standard uncertainties u are u(T) = 0.1 K; u(P) = 0.3 kPa; u(x1) = u(y1) = 0.0008. bAAD: see caption of Table 3.

Table 6. Parameters for Estimating Liquid Molar Volumes concentration ranges for K1-values, while for the K2-values,
(VL/m3 kmol−1) greater errors were observed. It could be assumed that the high
relative volatilities of the studied mixtures could result in small
GVL acetone ethyl acetate K1-value and higher K2-value errors (eq 8).
a 0.9868 1.2298 0.8996
Kcalc − Kexp
b 0.27532 0.2576 0.2586 K −value error =
c 727 508.2 523.3 Kexp (8)

■
d 0.349 0.29903 0.278

shows a great difference to the other models, which can also be
represented by the corresponding T−x−y plot. For the mixture
of ethyl acetate−GVL, all models show greater relative
volatilities; adequate fit is only observed at smaller x1
concentrations. These models were also compared with the
experimental data using the corresponding K-values (defined in
eq 5). The model K-value errors presented in the Supporting
Information (Figures S6−S11). In all the cases, the model
showed insignificant errors in the complete measured
E https://dx.doi.org/10.1021/acs.jced.9b00379
CONCLUSIONS
The isobaric vapor−liquid equilibria (VLE) of the binary
systems of GVL with water, acetone, and ethyl acetate were
investigated at p = 101.3 kPa using modified Gillespie still,
which was successfully applied before for mixtures having a
greater difference in their boiling points. Experimental data for
the mixtures of GVL with acetone and ethyl acetate were
correlated by Wilson, NRTL, and UNIQUAC models, and the
results were compared with UNIFAC and Raoult’s law
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Table 7. Calculated Parameters of Wilson (Aij; Aji: Binary Interaction Parameters, cal/gmol), NRTL (Bij; Bji: Binary
Parameters, K; αij, Nonrandomness Factor, Dimensionless), and UNIQUAC (ΔUij; ΔUji: Binary Interaction Parameter, cal/
gmol) Models
Wilson
Aij Aji Bij
acetone−GVL 264.05 −122.31 −185.42
ethyl acetate−GVL 114.44 158.10 −72.984
calculations. The results showed that γ-valerolactone can be
separated from both investigated components without the
formation of the azeotropic mixture. For analytical purposes,
the refractive indexes at T = 293.2 and 298.2 K were
determined in the whole concentration range for the binary
mixtures.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jced.9b00379.
Experimental refractive indexes for acetone−GVL and
ethyl acetate−GVL mixtures at 293.2 and 298.2 K
(Tables S1 and S2 and Figures S1 and S2); structural
parameters for the UNIFAC and UNIQUAC models for
pure components (Table S3); relative volatilities of
water−GVL, acetone−GVL, and ethyl acetate−GVL
mixtures (Figures S3−S5); and percentage errors of
model K-values (Figures S7−S11) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
László T. Mika − Department of Chemical and Environmental
Process Engineering, Budapest University of Technology and
Economics H-1111 Budapest, Hungary; orcid.org/0000-
0002-8520-0065; Phone: +36 1 463 1263;
Email: laszlo.t.mika@mail.bme.hu; Fax: +36 1 463 3197
Authors
Dávid Havasi − Department of Chemical and Environmental
Process Engineering, Budapest University of Technology and
Economics H-1111 Budapest, Hungary; orcid.org/0000-
0003-3366-4009
Dániel Farkas − Department of Chemical and Environmental
Process Engineering, Budapest University of Technology and
Economics H-1111 Budapest, Hungary
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jced.9b00379
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was funded by National Research, Development,
and Innovation Office, NKFIH (KH 129508) and by the
Higher Education Excellence Program of the Ministry of
Human Capacities in the frame of Biotechnology research area
of Budapest University of Technology and Economics (BME
FIKP-BIO). L.T.M. is grateful to the support of Scholarship of
József Varga Foundation, Budapest University of Technology
and Economics, Budapest, Hungary.
F https://dx.doi.org/10.1021/acs.jced.9b00379
pubs.acs.org/jced Article
NRTL UNIQUAC
Bji αij ΔUij ΔUji
1003.9 0.34775 35.579 −6.228
232.43 0.25468 412.40 −269.56
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