Journal of Chemical & Engineering Data Article

Article
Table 1. List of Chemicals Used in This Study and Their Respective Purities (p = 0.1 MPa)
pubs.acs.org/jced
refractive index density/gcm3
chemical supplier minimum purity claimed (mass %)a GC analysis (peak area %) expb litd expc litd
1-propanol Sigma-Aldrich 99.5 99.3 1.38512 1.3850 0.80366 0.8035
VaporLiquid Equilibrium for Methyl Isobutyl Ketone (MIBK) + (1- 2-Propanol Merck 99.5 99.4 1.37718 1.3776 0.78499 0.7855
MIBK Merck 99.0 99.8 1.39586 1.3962 0.80030 0.7978
Propanol or 2Propanol) Binary Mixtures a
As stated by the supplier. bRefractive index at 293.15 K, standard uncertainties u are u(T) = 0.01 K and u(nD) = 0.0004. cDensity at 293.15 K; u()
= 0.0005 gcm3 and u(T) = 0.03 K. dLiterature values for the refractive indices and density taken from Lide.9
Funmilola Avoseh, Samuel A. Iwarere, Caleb Narasigadu, and Deresh Ramjugernath*
Thermodynamics Research Unit, School of Engineering, University of KwaZulu-Natal, Durban 4041, South Africa and purities of the chemicals from the gas chromatograph are Table 2. Physical Properties and Parameters Used for the
presented in Table 1. Data Reduction in This Study
Apparatus and Procedure. The VLE measurements were
pure component property 1-propanol 2-propanol MIBK
ABSTRACT: Isothermal vaporliquid equilibrium (VLE) data for 1-propanol undertaken using a low pressure glass recirculating still that is
+ methyl isobutyl ketone at 338.15, 353.15, and 368.15 K and 2-propanol + described in previous publications.11,12 The VLE stills have Tc13/K 536.78 508.30 574.60
methyl isobutyl ketone were measured at 323.15, 338.15, and 353.15 K. All the been used extensively for low-pressure phase equilibria Pc13/kPa 5175 4762 3270
measurements were undertaken on a recirculating VLE glass still operated at measurements in the Thermodynamics Research Unit at the Vc13/cm3mol1 219.00 220.00 340.60
University of KwaZulu-Natal. The schematic diagram, compressibility factor (Zc)13 0.254 0.248 0.256
isothermal conditions. The experimental VLE data for all the measured binary 13
description of the apparatus, as well as the experimental acentric factor () 0.629 0.665 0.351
systems were correlated with the Wilson and NRTL activity coecient models
procedure are available in the previous publication.11,12 dipole moment13/debye 1.7 1.7 2.8
using the gammaphi approach () with the Hayden and OConnell
The equilibrium temperature was measured with a Pt-100 radius of gyration14,15/ 2.736 2.726 3.83
correlation employed for calculating the second virial coecients that are used
temperature sensor calibrated against a WIKA CTH 6500 Association (ii) and Solvation Parameters (ij)15
in accounting for nonidealities in the vapor phase. The models provided
standard temperature sensor. The Pt-100 sensor was connected n-PrOH 1.40 1.55 1.0
satisfactory correlation of the measured alcoholketone-binary mixtures at all
to a Hewlett-Packard 6 1/2 digit multimeter with has a 0.004% i-PrOH 1.55 1.32 1.0
the temperatures reported. The thermodynamic consistency of the data was
claimed accuracy, equivalent to 0.005 ohms in the measurement MIBK 1.0 1.0 0.9
checked using the point test method of Van Ness et al. (Van Ness, H. C.; Byer,
range, which translates to an uncertainty of 0.013 K. The digital A 16.349 16.425 14.819
S. M.; Gibbs, R. E. AIChE J. 1973, 19, 238244) as well as the more rigorous
multimeter enables the resistance of the sensor to be displayed B 3592.820 3462.439 3519.985
direct test of Van Ness (Van Ness, H. C. Pure Appl. Chem. 1995, 67, 859872).
and then converted to temperature in Kelvin using a calibration C 209.422 210.989 229.739
equation. Taking into account uncertainty from the calibration
INTRODUCTION state for the vapor phase nonideality. The measured data were along with other sources of error in measuring the temperature,
the combined uncertainty in the temperature measurement is coecients for the MIBK + (1-propanol or 2-propanol)
further subjected to thermodynamic consistency testing using

The extensive use of methyl isobutyl ketone (MIBK) makes it
an important chemical in the petrochemical industry. This
ketone is generally used as an industrial solvent. Methyl
isobutyl ketone is further used as a chemical intermediate in the
production of paints, rubber products, chemicals, and drugs.
Ketones are constituent components found in the waste stream
of the FischerTropsch process, generally together with
alcohols.3 Thermodynamic knowledge on the separation and
purication of these alcohols + ketones binary mixtures is
required as this helps in designing and optimizing the process
plants in which they are found.
There are isothermal VLE data available in the open
literature4 for MIBK + 2-butanol system at 368 K, MIBK +
tert-pentanol at 294, 338, and 368 K, and MIBK + 2-ethyl-1-
hexanol at 388 K. There are also extensive isobaric VLE data by
Beatriz et al.5 for MIBK + cyclohexane and cyclohexene at 100
kPa. Ballard and Van Winkle6 reported measured isobaric VLE
data for 2-propanol + methyl isobutyl ketone at 760 mmHg,
while VLE binary data sets for 2-propanol + methyl isobutyl
ketone at 330.0 and 340.0 K were reported by Psutka and
Wichterle.7
In this work, isothermal VLE data were measured for 1-
propanol + MIBK at 338.15, 353.15, and 368.15 K and 2-
propanol + MIBK at 323.15, 338.15, and 353.15 K. Beyond the
2-propanol + MIBK system mentioned above, the authors are
not aware of any other VLE data available in open literature for
these systems.
The newly measured VLE data were regressed using the
combined gamma-phi () method with the NRTL and
Wilson activity coecient models to account for the liquid
phase nonideality and the Hayden and OConnell8 correlation
to calculate the second virial coecient in the virial equation of
XXXX American Chemical Society
the point test1 and direct test.2
EXPERIMENTAL SECTION
Chemicals. Methyl isobutyl ketone (CAS No. 108-10-1)
and 2-propanol (CAS No. 67-63-0) were purchased from
Merck, while 1-propanol (CAS No. 71-23-8) was purchased
from Sigma-Aldrich. Purity checks were performed on each
chemical before commencing with experimental measurements.
The purity of these chemicals was checked by means of gas
chromatographic analysis, as well as refractive index and density
measurements. The refractive index of each chemical was
measured at 293.15 K using the ATAGO 7000 refractometer
with a reported standard uncertainty of 0.0001. The results
were compared with refractive index values in the literature.
The density () of each chemical was measured using the
Anton Paar DMA 5000 densitometer with a reported standard
uncertainty of 0.0005 g/cm3 in density and 0.03 K in
temperature. According to the information provided by the
manufacturer (Anton Paar),10 the DMA 5000 density meter has
an accuracy and repeatability of 0.000005 and 0.0000001 g/
cm3 for density, respectively, and a temperature accuracy of
0.01 K and temperature repeatability of 0.001 K. The density
values measured were compared with literature at 293.15 K.
There was no further purication of the reagents as no
signicant impurities were found. The refractive index values
Received: January 10, 2017
Accepted: May 13, 2017
A DOI: 10.1021/acs.jced.7b00026
J. Chem. Eng. Data XXXX, XXX, XXXXXX
estimated to be 0.18 K. A WIKA model P10 pressure
transmitter was used to measure the system pressure. This
pressure transmitter has a pressure range of 0 to 1 bar. This is
in line with the maximum pressure limit of 101 kPa, for the
dynamic recirculating glass still of Joseph et al.11,12 The
combined standard uncertainty, U(p), in the pressure measure-
ment was estimated to be 0.1 kPa.
A Shimadzu 2014 gas chromatograph (GC-2014) equipped
with a thermal conductivity detector was used to undertake the
composition analyses with a CRS Porapak Q column. Helium
gas was used as the carrier gas. The packed column is 4 m in
length with an inner diameter of 2 mm. The maximum
allowable operating temperature of the column is 250 C. The
equilibrium samples were withdrawn from the sample traps
using a 0.5 L gastight GC syringe, once the system is deemed
to have attained equilibrium. In this study, equilibrium was
assumed to have been reached when the pressure remained
constant for about 45 min. Samples were taken in triplicate for
the determination of the liquid and vapor compositions. The
combined standard uncertainty for both the liquid and vapor
compositions is 0.002 mole fraction.
DATA REDUCTION OF NEWLY MEASURED VLE
SYSTEMS
The measured (Pxy) VLE data for the ketonealcohol
binary mixtures were regressed with the combined
method using the pure component properties listed in Table
2. The NRTL and Wilson liquid phase activity coecient
equations were used to account for any deviations from ideality
in the liquid phase. For describing the vapor phase nonideality,
the virial equation of state was used employing the Hayden and
OConnell8 correlation for the calculation of the second virial
B DOI: 10.1021/acs.jced.7b00026
systems. Unlike methyl isobutyl ketone, 1-propanol and 2-
propanol have the tendency for self-association. Thus, the
Hayden and OConnell correlation uses a parameter to describe
chemical association between the binary mixtures, which is
dependent on the type of functional group the components are
categorized. The association parameters used in this study were
taken from Fredenslund et al.14 and Prausnitz et al.15
The Hayden and OConnell correlation approach is reliable
at low to moderate pressure for describing the behavior of two
polar binary mixtures in the vapor phase because mixing rules
are employed for predicting the cross coecients, and
association and solvation eect is accounted for. The liquid
phase activity coecient (i) was calculated for the ketone
alcohol system using the conventional equilibrium condition for
the approach presented in eq 1
yi iP = xiipisat (i = 1, 2) (1)
where xi and yi are the measured liquid phase and vapor phase
mole fractions, respectively, P is the system pressure, pisat is the
saturated vapor pressure for the pure component i at the
system temperature T, and i is the activity coecient.
The term (i) is given as follows
V (ViL /cm 3mol1)
i = isat exp 3 1 1
(Pisat /kPa P /kPa)
i (R /kPacm mol K )(T /K)
(2)
where vi is the fugacity coecient for the vapor phase, sat
i is
the fugacity coecient for the saturated vapor phase of the pure
component, R is the universal gas constant, and VLi is the molar
volume of the liquid phase. The truncated two term virial
equation of state was employed for the computation of the pure
component and mixture fugacity coecients. The Rackett
J. Chem. Eng. Data XXXX, XXX, XXXXXX
Journal of Chemical & Engineering Data Article Journal of Chemical & Engineering Data Article

correlation16 was employed for the estimation of liquid molar Table 3. Experimental Boiling Point Temperatures (Texp) Table 5. VaporLiquid Equilibrium Dataa for Pressure (P), Table 7. VaporLiquid Equilibrium Dataa for Pressure (P),
volumes. and Literature Temperatures (Tlit) for 1-Propanol, 2- Liquid-Phase Mole Fraction (x1), Vapor Phase Mole Liquid-Phase Mole Fraction (x1), Vapor Phase Mole
Propanol, and Methyl Isobutyl Ketone at Its Saturated Vapor Fraction (y1), and Activity Coecients (1, 2) for 1- Fraction (y1), and Activity Coecients (1, 2) for 2-
RESULTS AND DISCUSSION Pressure (P)a Propanol (1) + Methyl Isobutyl Ketone (2) at T = 353.15 K Propanol (1) + Methyl Isobutyl Ketone (2) at T = 323.15 K
The vapor pressures for the three components used in this P/kPa Texp/K Tlit./Kb T/Kc P/kPa x1 y1 1 2 P/kPa x1 y1 1 2
study were measured and compared with the literature
1-Propanol 31.41 0.000 0.000 1.000 9.22 0.000 0.000 1.000
values1719 as shown in Figure 1. The vapor pressures for 1-
14.90 326.98 327.16 0.18 37.91 0.110 0.230 1.559 1.029 12.76 0.097 0.323 1.809 1.013
25.89 338.09 338.36 0.27 41.61 0.209 0.362 1.420 1.055 15.07 0.194 0.490 1.640 1.022
29.90 341.12 341.43 0.31 44.45 0.300 0.455 1.320 1.081 16.76 0.268 0.579 1.541 1.020
39.89 347.45 347.77 0.32 46.03 0.377 0.523 1.254 1.105 17.95 0.342 0.625 1.400 1.085
51.21 353.14 353.50 0.36 47.29 0.442 0.568 1.192 1.147 19.52 0.459 0.681 1.235 1.221
59.89 356.86 357.21 0.35 48.18 0.495 0.607 1.158 1.174 20.99 0.601 0.752 1.120 1.383
69.89 360.59 360.95 0.36 49.76 0.645 0.696 1.057 1.341 21.67 0.677 0.798 1.087 1.435
79.88 363.91 364.27 0.36 50.66 0.729 0.747 1.018 1.484 22.30 0.760 0.838 1.046 1.594
93.89 368.02 368.37 0.35 51.26 0.796 0.808 1.016 1.508 22.91 0.843 0.887 1.022 1.741
99.88 369.61 369.97 0.36 51.66 0.843 0.845 1.006 1.588 23.14 0.899 0.920 1.007 1.942
2-Propanol 51.64 0.886 0.885 1.004 1.625 23.39 0.953 0.958 0.999 2.214
14.90 314.43 314.47 0.04 51.54 0.936 0.931 0.999 1.737 23.48 1.000 1.000 1.000
23.43 323.03 323.01 0.02 51.00 1.000 1.000 1.000 a
U(T) = 0.15 K (k = 2); U(P) = 0.1 kPa (k = 2); U(x, y) = 0.002 (k =
29.90 327.97 327.87 0.10 a
U(T) = 0.15 K (k = 2); U(P) = 0.1 kPa (k = 2); U(x, y) = 0.002 (k = 2).
39.89 333.98 333.87 0.11 2).
48.34 338.14 338.03 0.11 Table 8. VaporLiquid Equilibrium Dataa for Pressure (P),
59.89 342.90 342.83 0.07 Table 6. VaporLiquid Equilibrium Dataa for Pressure (P), Liquid-Phase Mole Fraction (x1), Vapor Phase Mole
Figure 1. Experimental vapor pressures of 1-propanol (), 2-propanol 69.89 346.45 346.40 0.05 Liquid-Phase Mole Fraction (x1), Vapor Phase Mole Fraction (y1), and Activity Coecients (1, 2) for 2-
(), and MIBK () compared with literature values of (),14 (),15
79.88 349.64 349.57 0.07 Fraction (y1), and Activity Coecients (1, 2) for 1- Propanol (1) + Methyl Isobutyl Ketone (2) at T = 338.15 K
and ()16 for 1-propanol, 2-propanol, and MIBK, respectively.
92.40 353.14 353.10 0.04 Propanol (1) + Methyl Isobutyl Ketone (2) at T = 368.15 K
98.88 354.82 354.78 0.04 P/kPa x1 y1 1 2
propanol, 2-propanol, and methyl isobutyl ketone were P/kPa x1 y1 1 2 17.57 0.000 0.000 1.000
Methyl Isobutyl Ketone
measured in the temperature ranges of 327369.6, 314.4 54.04 0.000 0.000 1.000 28.92 0.190 0.486 1.538 1.020
9.22 322.82 322.95 0.13
354.8, and 322.8376.4 K, respectively. The measured vapor 9.90 324.41 324.51 0.10 63.68 0.111 0.220 1.364 1.042 32.18 0.275 0.561 1.375 1.090
pressures for 1-propanol, 2-propanol, and methyl isobutyl 17.52 337.85 337.83 0.02 70.25 0.206 0.365 1.342 1.046 38.07 0.460 0.688 1.186 1.224
ketone were found to be in good agreement with the Antoine 18.41 339.11 339.05 0.06 76.25 0.300 0.464 1.255 1.072 41.39 0.594 0.771 1.114 1.294
coecients given by the authors such as Kemme and Kreps,17 31.36 352.88 352.94 0.06 79.52 0.375 0.527 1.190 1.107 43.03 0.675 0.814 1.076 1.365
or the Antoine coecients calculated by NIST from 32.13 353.54 353.61 0.07 82.17 0.442 0.577 1.141 1.145 44.68 0.756 0.854 1.043 1.477
Biddiscombe et al.18 and Fuge et al.s19 data as reported on 39.89 359.60 359.69 0.09 84.15 0.497 0.617 1.110 1.176 46.13 0.841 0.898 1.018 1.636
the NIST Chemistry WebBook20 with deviations from 53.99 368.46 368.67 0.21 89.97 0.739 0.769 1.001 1.473 46.91 0.895 0.927 1.005 1.806
literature as reported in Table 3. The maximum relative errors 69.89 376.36 376.78 0.42 91.80 0.811 0.821 0.988 1.601 47.71 0.950 0.963 1.000 1.955
are 0.10% for 1-propanol, 0.03% for 2-propanol, and 0.11% for a 92.57 0.850 0.858 0.992 1.612 48.45 1.000 1.000 1.000
U(T) = 0.15 K (k = 2); U(P) = 0.1 kPa (k = 2); U(x, y) = 0.002 (k =
methyl isobutyl ketone. The experimental vapor pressure data 93.43 0.892 0.897 0.995 1.635 a
2). bNIST Chemistry WebBook.20 cT/K = (Texp Tlit). U(T) = 0.15 K (k = 2); U(P) = 0.1 kPa (k = 2); U(x, y) = 0.002 (k =
were regressed to obtain the Antoine parameter constants (A, 93.90 0.937 0.939 0.997 1.671 2).
B, C) presented in Table 2 using eq 3. The obtained values a 93.92 1.000 1.000 1.000
Table 4. VaporLiquid Equilibrium Data for Pressure (P),
were used in the VLE data reduction algorithm a Table 9. VaporLiquid Equilibrium Dataa for Pressure (P),
Liquid-Phase Mole Fraction (x1), Vapor Phase Mole U(T) = 0.15 K (k = 2); U(P) = 0.1 kPa (k = 2); U(x, y) = 0.002 (k =
B Fraction (y1), and Activity Coecients (1, 2) for 1- 2). Liquid-Phase Mole Fraction (x1), Vapor Phase Mole
ln pisat /kPa = A (i = 1, 2) Fraction (y1), and Activity Coecients (1, 2) for 2-
T /K + C 273.15 (3) Propanol (1) + Methyl Isobutyl Ketone (2) at T = 338.15 K
Propanol (1) + Methyl Isobutyl Ketone (2) at T = 353.15 K
VLE were measured at isothermal conditions for the 1- P/kPa x1 y1 1 2 VLE binary systems show positive deviations from Raoults law
propanol + MIBK and 2-propanol + MIBK systems with 17.57 0.000 0.000 1.000 with the 1-propanol + MIBK system exhibiting a maximum P/kPa x1 y1 1 2
correlation of the data with two liquid-phase activity coecient 21.32 0.114 0.229 1.651 1.038 pressure azeotrope for the 338.15 and 353.15 K isotherms. The 31.41 0.000 0.000 1.000
models, namely Wilson and NRTL equations. The Marquardt 23.11 0.202 0.359 1.581 1.037 experimental azeotropic composition, x1AZ,exp and pressure 42.51 0.099 0.301 1.425 1.030
method21 with an objective function that minimizes the square 24.53 0.304 0.444 1.380 1.096 PAZ,exp for the 1-propanol + MIBK system in this study were 61.56 0.336 0.618 1.246 1.101
root of the sum of the squares of the deviations in pressure and 25.16 0.375 0.499 1.295 1.133 obtained by the numerical smoothing of the (x1y1) versus x1 65.66 0.399 0.671 1.211 1.114
vapor phase composition was used for the tting of the Wilson 25.81 0.445 0.556 1.243 1.157 and Px1 curves, which according to Pavl cek and Wichterle22 69.08 0.455 0.710 1.178 1.135
and NRTL parameters. The Pxy data along with the 26.09 0.499 0.587 1.186 1.208 is better than using correlative procedures. The azeotropic 76.20 0.590 0.789 1.108 1.205
experimental activity coecients are listed in Tables 49 for 26.61 0.635 0.677 1.100 1.327 compositions for each isotherm are shown in Table 10. 79.66 0.670 0.827 1.070 1.284
the measured binary systems. The Pxy plots for the 1- 26.95 0.707 0.727 1.067 1.406 Representative plots of the activity coecients (1, 2) for 2- 83.35 0.756 0.866 1.037 1.405
propanol + MIBK binary mixture at 338.15, 353.15, and 368.15 26.98 0.792 0.788 1.033 1.540 propanol (1) + MIBK (2) and 1-propanol (1) + MIBK (2) at 86.70 0.839 0.907 1.016 1.534
K are shown in Figure 2. For the 2-propanol + MIBK system, 26.94 0.839 0.827 1.020 1.620 323.15 and 338. 15 K are shown in Figures 4 and 5, 88.57 0.895 0.936 1.006 1.657
the Pxy plots at 323.15, 338.15, and 353.15 K are shown in 26.84 0.888 0.872 1.010 1.713 respectively. The activity coecients in Figures 4 and 5 are 90.61 0.948 0.969 1.003 1.655
Figure 3. 26.46 0.953 0.942 1.003 1.827 plotted alongside those calculated using the NRTL equation 92.48 1.000 1.000 1.000
a
In modeling the 1-propanol + MIBK and 2-propanol + 25.92 1.000 1.000 1.000 and found to be well-represented by the NRTL Gibbs excess U(T) = 0.15 K (k = 2); U(P) = 0.1 kPa (k = 2); U(x, y) = 0.002 (k =
MIBK binary systems, the vapor phase nonideality was taken model. The Wilson equation gave similar results to the NRTL 2).
a
into account using the second virial coecients obtained from U(T) = 0.15 K (k = 2); U(P) = 0.1 kPa (k = 2); U(x, y) = 0.002 (k = equation for the calculation of the activity coecients and
the Hayden and OConnell correlation equation. The measured 2). hence only one of the models was used for the representative
C DOI: 10.1021/acs.jced.7b00026 D DOI: 10.1021/acs.jced.7b00026
J. Chem. Eng. Data XXXX, XXX, XXXXXX J. Chem. Eng. Data XXXX, XXX, XXXXXX
Journal of Chemical & Engineering Data Article Journal of Chemical & Engineering Data Article

Table 11. Model Parameters (g12, g21, and 12 for NRTL

Model); (12 and 21 for Wilson Model) and Average
Absolute Deviations for the Correlation of the {1-Propanol
(1) + Methyl Isobutyl Ketone (2)} and {2-Propanol (1) +
Methyl Isobutyl Ketone (2)} VLE Data to NRTL and Wilson
Modelsa
model newly measured binary mixtures
NRTL T/K = 338.15 T/K = 353.15 T/K = 368.15
1-Propanol (1) + Methyl Isobutyl Ketone (2)
g12/(J mol1) 764.43 534.80 427.93
g21/(J mol1) 1497.51 1462.16 1285.44
12 0.47 0.47 0.47
y1 0.004 0.006 0.012
Figure 4. Comparison of experimental (, ) liquid phase activity P /kPa 0.074 0.140 0.288
Figure 2. Px1y1 VLE data for 1-propanol (1) + MIBK (2) at (from coecients (1, 2) and those calculated using NRTL model () for RMS ln(1/2) 0.036 0.044 0.094 Figure 7. Direct test for thermodynamic consistency for 1-propanol
bottom to top) T = 338.15, 353.15, and 368.15 K: (, ), the 2-propanol + MIBK (2) system at 323.15 K. Wilson (1) + MIBK (2) system at 338.15 K.
experimental values; (), calculated from regressed NRTL parameters. 12/(J mol1) 2685.46 2687.11 2532.72
21/(J mol1) 405.83 676.01 811.50
y1 0.004 0.006 0.012
P /kPa 0.073 0.138 0.286
RMS ln(1/2) 0.040 0.050 0.102
NRTL T/K = 323.15 T/K = 338.15 T/K = 353.15
2-Propanol (1) + Methyl Isobutyl Ketone (2)
g12/(J mol1) 1466.82 1343.70 1664.00
g21/(J mol1) 834.25 709.50 147.33
12 0.47 0.47 0.47
y1 0.005 0.005 0.006
P /kPa 0.043 0.076 0.107
RMS ln(1/2) 0.040 0.045 0.043
Wilson
12/(J mol1) 1937.07 1848.41 1321.74
Figure 5. Comparison of experimental (, ) liquid phase activity 21/(J mol1) 380.84 217.23 500.16
y1 0.005 0.005 0.006 Figure 8. Comparison and prediction of Pxy diagram for the 2-
coecients (1, 2) and those calculated using NRTL model () for
Figure 3. Px1y1 VLE data for 2-propanol (1) + MIBK (2) at (from P/kPa 0.044 0.075 0.104 propanol (1) + MIBK (2) system. Experimental: , , this work at
the 1-propanol (1) + MIBK (2) system at 338.15 K.
bottom to top) T = 323.15, 338.15, 353.15 K: (, ), experimental RMS ln(1/2) 0.040 0.045 0.044
323.15 and 338.15 K; , , 330.0 K and , , 340.0 K, Psutka and
values; (), calculated from regressed NRTL parameters. a
Wichterle;7 , NRTL model for this work; ----, NRTL model for
representative plot of the point test for the 2-propanol + MIBK P/kPa = 1/nin|Piexp Picalc|; y = 1/nin|yiexp yicalc|. Psutka and Wichterle.7
Table 10. Experimental Azeotropic Composition x1AZ,exp and system at 323.15 K is shown in Figure 6.
pressure PAZ,exp for 1-Propanol (1) + Methyl Isobutyl Ketone The use of the more rigorous Van Ness2 direct test for
(2) System thermodynamic consistency check for all the measured VLE ThermoData Engine (TDE) software implemented in
data fall within the consistency index of 2 for the RMS ln(1/ ASPEN24 and the prediction using parameters obtained by
T/K x1AZ,exp PAZ,exp (kPa) 2), with the exception of the 1-propanol + MIBK binary regressing the VLE data of Psutka and Wichterle.7 According to
338.15 0.780 26.98 mixture at 368.15 K which falls under the consistency index of the prediction using the regressed binary parameters from
353.15 0.872 51.65 3 as reported in Table 11. The NRTL and Wilson models tted literature, the relative deviations of the pure component vapor
368.15 0.995 93.92 the data suciently well and only marginal dierences could be pressure were 0.19% and 0.28% for the MIBK at 323.15 and
observed from the results of both models, as can be seen in 338.15 K, respectively. The relative deviations of the pure
Table 10. An example of the Van Ness2 consistency direct test component vapor pressure for 2-propanol was 1.42% and
plots shown in Figures 4 and 5. The regressed NRTL and is shown in Figure 7 for the 1-propanol + MIBK system at 1.39% at 323.15 and 338.15 K, respectively. When the pure
Wilson parameters for all the measured VLE data are reported 338.15 K. component vapor pressures for the 2-propanol and MIBK in
in Table 11. Comparisons and Predictions. The only data sets this study were revaluated at 323.15 and 338.15 K using the
Although, the thermodynamic consistency test does not available for comparison with the experiments in this study NIST TDE software, the relative deviations obtained were
conrm the correctness of the measured data, it is a test that are those of Psutka and Wichterle7 for 2-propanol + MIBK. 0.21% and 0.42% for the MIBK at 323.15 and 338.15 K,
is deemed necessary in validating the quality and the degree of However, no direct comparison is possible because their data respectively, and the values for 2-propanol were 0.49% and
Figure 6. Point test for thermodynamic consistency for 2-propanol (1)
reliability of the measured data. According to Danner and were at 330.0 and 340.0 K. Therefore, in order to demonstrate 0.52% at 323.15 and 338.15 K, respectively.
+ MIBK (2) system at 323.15 K.
Gess,23 VLE data is deemed to be thermodynamically the reliability of the experimental data and modeling procedure
consistent if the absolute deviation between the experimental for the new binary data sets, the data from Psutka and CONCLUSIONS
vapor phase composition and its calculated values obtained Wichterle7 at both temperatures of 330.0 and 340.0 K were predictions using the NRTL two parameter Gibbs excess Three isothermal VLE data sets were each measured for the 1-
through Van Ness et al.1 point test is 0.01 mole fraction. regressed using the NRTL two parameter Gibbs excess model models from the data of Psutka and Wichterle7 to this study propanol + MIBK and 2-propanol + MIBK systems,
Thus, the average absolute values for the vapor phase with xed at 0.47 as in this study. The regressed parameters presented in Figure 8 shows that the model predictions for 2- respectively. All six isotherms were successfully correlated
composition (y1) reported in Table 11 was found to satisfy were then used in predicting the Pxy diagram at propanol + MIBK based on this study compare reasonably well. using a combination of the NRTL and Wilson liquid phase
the consistency criterion recommended by Danner and Gess23 temperatures of 323.15 and 338.15 K, which are close to the Comparisons were made between the 2-propanol and MIBK Gibbs excess models with the Hayden and OConnell
for all the measured binary systems, except the 1-propanol + temperatures of 330.0 and 340.0 K reported for 2-propanol + pure component vapor pressures in this study and those correlation for calculating the second virial coecients. The
MIBK binary mixture at 368.15 K that has a y1 of 0.012. A MIBK by Psutka and Wichterle.7 The results from the obtained by re-evaluating vapor pressures using the NIST 1-propanol + MIBK system exhibited an azeotrope at 338.15
E DOI: 10.1021/acs.jced.7b00026 F DOI: 10.1021/acs.jced.7b00026
J. Chem. Eng. Data XXXX, XXX, XXXXXX J. Chem. Eng. Data XXXX, XXX, XXXXXX
Journal of Chemical & Engineering Data Article

and 353.15 K. Experimental values of the activity coecients
for the 1-propanol + MIBK and 2-propanol + MIBK systems
obtained using the traditional approach compared well with
those obtained from the NRTL and Wilson equation. The
measured VLE data were found to be thermodynamically
consistent based on the point test of Van Ness et al.1 In
addition, the use of the rigorous direct test of Van Ness2 gave
good RMS values for the residuals ln(1/2) for both the 1-
propanol + MIBK and 2-propanol + MIBK systems.
AUTHOR INFORMATION
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Corresponding Author
*E-mail: ramjuger@ukzn.ac.za. Tel: +27 (0)31 2603128. and 4-methyl-2-pentanone. Fluid Phase Equilib. 2005, 235, 5863.
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Samuel A. Iwarere: 0000-0001-8566-6773 isobutyl ketone systems. Ind. Eng. Chem. 1953, 45, 18031804.
Deresh Ramjugernath: 0000-0003-3447-7846 (8) Hayden, J. G.; OConnell, J. P. Generalized Method for
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Handbook of Chemistry and Physics; 76th ed.; CRC Press: Boca Raton,
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Technology and National Research Foundation for the nancial anton-paar.com/corp-en/products/details/density-meters-dma-
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G DOI: 10.1021/acs.jced.7b00026
J. Chem. Eng. Data XXXX, XXX, XXXXXX