J. Chem.

Thermodynamics 45 (2012) 8389

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Isothermal (vapour + liquid) equilibria in the binary and ternary systems

composed of 2-propanol, 2,2,4-trimethylpentane, and 2,4-dimethyl-3-pentanone
Jan Pavlcek, Ivan Wichterle
Institute of Chemical Process Fundamentals v.v.i., Academy of Sciences of the Czech Republic, Rozvojov 135, 165 02 Praha 6, Czech Republic

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

Article history: (Vapour + liquid) equilibrium data in the three binary (2-propanol + 2,2,4-trimethylpentane), (2-propa-
Received 31 May 2011 nol + 2,4-dimethyl-3-pentanone), (2,2,4-trimethylpentane + 2,4-dimethyl-3-pentanone) systems, and in
Received in revised form 8 September 2011 the ternary (2-propanol + 2,2,4-trimethylpentane + 2,4-dimethyl-3-pentanone) system are reported.
Accepted 13 September 2011
The data were measured isothermally at (330.00 and 340.00) K covering the pressure range (8 to
Available online 17 September 2011
70) kPa. The binary (vapour + liquid) equilibrium data were correlated using the Wilson and NRTL equa-
tions by means of a robust algorithm for processing all isotherms together; resulting parameters were
Keywords:
then used for calculation of phase behaviour in the ternary system and for subsequent comparison with
(Vapour + liquid) equilibrium
Experimental data
experimental data. Azeotropic behaviour of the (2-propanol + 2,2,4-trimethylpentane) system was eval-
Prediction uated together with all available published data.
Alcohol 2011 Elsevier Ltd. All rights reserved.
Hydrocarbon
Ketone
Azeotropic behaviour

1. Introduction measured at the two constant temperature levels, particularly at

New results of a continuing project dealing with (vapour + li-
quid) equilibria (VLE) in mixtures belonging to distinct families
of organic compounds are reported in this paper. (Vapour + liquid)
equilibria are determined for three binary and one ternary systems
containing alcohol, hydrocarbon and ketone. Within the series of
papers, the systems of components having a common alkyl group
(isopropyl or tert-butyl), namely (2-propanol + diisopropyl ether + 2,
2,4-trimethylpentane) [1], (tert-butanol + 2,2,4-trimethylpentane +
1-tert-butoxy-2-propanol) [2], (tert-butyl methyl ether + tert-buta-
nol + 2,2,4-trimethylpentane) [3], (2-propanol + diisopropyl ether +
1-methoxy-tert-butyl methyl ether) [4], (2-propanol + diisopropyl
ether + 4-methyl-2-pentanone) [5], (2-methylpentane + 3-methyl-
2-butanone + 3-methyl-2-butanol) [6], (2-propanol + 3-methyl-2-
butanone + 2,2,4-trimethylpentane) [7], (tert-butyl methyl ether + 3,
3-dimethyl-2-butanone + 2,2-dimethyl-1-propanol) [8], and (2,2,4-
trimethylpentane + 2-methyl-1-propanol + 4-methyl-2-pentanone)
[9] have already been investigated. On concluding of such exten-
sive experimental studies, the processing of this database would
result, e.g. in evaluation of better parameters for group contribu-
tion methods.
Compounds used in this paper contain also both isopropyl, hy-
droxyl, and carboxyl groups, namely in 2-propanol, 2,2,4-trimeth-
ylpentane, and 2,4-dimethyl-3-pentanone. The new data were
Corresponding author. Tel.: +420 220 390 289; fax: +420 220 920 661.
E-mail address: wi@icpf.cas.cz (I. Wichterle).
(330.00 and 340.00) K in order to be compatible with previous
measurements.
2. Experimental
2.1. Apparatus and procedure
Experimental VLE data were measured in an all glass circulation
still chargeable with 150 ml of liquid phase; essentially, it was the
DvorakBoublk type which is quoted in our previous papers (e.g.
[7]). The pressure was measured indirectly via the boiling point
of water in an ebulliometer connected in parallel to the still; the
uncertainty is 0.1% of the measured value. The equilibrium tem-
perature was determined with the digital thermometer F250
(ASL, United Kingdom) calibrated against a Pt-resistance thermom-
eter traceable to the NBS (Washington, DC, USA) certicate (1962),
however, the basic resistance is regularly re-checked by the triple
point of water; the absolute uncertainty of temperature measure-
ment (on ITS-90 scale) was estimated as 0.02 K. Samples with-
drawn for gas chromatographic (GC) analysis were kept in a
desiccator lled with silica gel because of their hygroscopicity.
Liquid-phase and vapour-phase compositions in all systems were
determined using a gas chromatograph HP6850 (HewlettPackard)
with thermal conductivity detection. The estimated uncertainty of
the composition measurement is better than 0.001 mole fraction.
Density was measured with a vibrating tube densimeter DMA 58
(A. Paar, Austria) with accuracy 0.00001. The refractive index

0021-9614/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2011.09.007
84 J. Pavlcek, I. Wichterle / J. Chem. Thermodynamics 45 (2012) 8389

TABLE 1
Properties of pure components.

Component 298:15 Reference 298:15 Reference

d4 =g  cm3 nD

2-Propanol 0.78091 This work 1.37504 This work

0.780860.78095 [10] 1.3752 [11]
0.78126 [11] 1.37509 [13]
0.78101 [13] 1.37515 [14]
0.78116 [14]
2,2,4-Trimethylpentane 0.68779 This work 1.38894 This work
0.68781 [11] 1.38898 [11]
0.687730.68778 [10] 1.388931.38915 [10]
0.68773 [13] 1.38887 [13]
0.68795 [14] 1.38916 [14]
2,4-Dimethyl-3-pentanone 0.79880 This work 1.3974 This work
0.79863 [11] 1.39759 [11]
0.7986 [12] 1.3976 [12]

was determined using the precise Abbe type refractometer TABLE 2

(Bellingham & Stanley, UK) with accuracy 0.00002. Saturated vapour pressures of 2,4-dimethyl-3-pentanone.

T/K p/kPa
2.2. Materials 330.00 8.87
330.04 8.87
2-Propanol [isopropanol] (Fluka AG, Buchs, Switzerland), puriss, 331.02 9.28
337.07 12.02
p.a. grade, declared purity of mass fraction P0.998, was used with-
340.00 13.55
out further purication. Molecular sieve 4A was used to remove 340.05 13.58
water. Purity determined by GC was 0.9994 mass fraction. 340.57 13.89
2,2,4-Trimethylpentane [isooctane] (Fluka AG), puriss. p.a. ACS 343.73 15.78
material, declared purity of mass fraction >0.995 was used as re- 347.76 18.48
351.12 21.02
ceived after being dried (and stored) over 4A molecular sieve.
365.80 35.36
The purity determined by GC was mass fraction 0.9995. 371.23 42.49
2,4-Dimethyl-3-pentanone [diisopropyl ketone] (Fluka AG, Buc- 373.22 45.36
hs, Switzerland), purum, declared purity of mass fraction P0.970 375.59 49.00
378.26 53.37
was fractionally rectied on 30-plate packed column and stored
381.01 58.22
over 4A molecular sieve. The purity determined by GC was mass 382.94 61.82
fraction 0.9938. 384.94 65.74
Properties of pure components and comparison with literature
Standard uncertainties u are u(T) = 0.01 K and u(p) = 0.01 kPa.
data are presented in table 1. Vapour pressures at normal boiling
point were not determined.
(2) The NRTL equation
3. Results " #
 2
G21 s12 G12
At rst, vapour pressure of pure 2,4-dimethyl-3-pentanone was
ln c1 x22 s21 ; 2
x1 x2 G21 x2 x1 G12 2
measured in the same experimental set-up. The experimental data
are summarised in table 2; they were correlated by the Antoine where G12 = exp[a12s12], G21 = exp[a21s21] and s12 = (g12  g22)/
equation with use of the maximum likelihood method. The stan- RT, s21 = (g21  g11)/RT. The equation contains three adjustable
dard deviations necessary for calculation were estimated as parameters, namely (g12  g22), (g21  g11), and a12 = a21.
0.01 K for temperature and 0.05% of the measured value for pres- Vapour phase imperfection and variation of the Gibbs free en-
sure. The resulting equation is log(p/kPa) = 6.513349  1486.166/ ergy of the pure liquid components with pressure were accounted
[(T/K)  64.804]; standard deviations in temperature and pressure for in terms of the second virial coefcients and the molar volumes
are 0.018 K and 0.049 kPa, respectively. under saturation pressure estimated, respectively, by the method
The direct experimental xyp values together with the activity of Hayden and OConnell [15] and of Hougen and Watson [16].
coefcients, c1, c2, and DGE (evaluated from the NRTL correlation) The adjustable parameters for binary systems were evaluated with
for all binary systems are given in table 3. The data were correlated use of the programme based on the maximum likelihood proce-
using the Wilson and NRTL equation in the forms as follows dure [17] which was modied by Pavlcek [18]. This new robust
(expressions for Inc2 can be easily obtained after interchanging algorithm makes it possible to correlate VLE isotherms or isobars
indices 1 and 2): together resulting in one set of universal parameters valid in the
(1) The Wilson equation experimental pressure and temperature range. It can be applied
x1 x2 A21 to any correlation equation with temperature independent param-
ln c1 1  lnx1 x2 A12   ; 1 eters such as, e.g. the Wilson or NRTL equations.
x1 x2 A12 x2 x1 A21
Within the correlation procedure [17], the experimental vapour
where A12 = (V2/V1)exp[(k12  k11)/RT], A21 = (V1/V2)exp[(k21  k22)/ pressures of the pure components were used instead of a vapour
RT] and Vi is liquid molar volume of pure component i. The concen- pressure equation for calculations, which is a procedure generally
tration dependence of the activity coefcient contains two adjust- recognised and recommended for isothermal data. It can be rea-
able parameters (k12  k11) and (k21  k22). lised by adjustment of the parameter A in the Antoine equation
 J. Pavlcek, I. Wichterle / J. Chem. Thermodynamics 45 (2012) 8389 85

TABLE 3
(Vapour + liquid) equilibrium experimental data and calculated (NRTL) activity coefcients c with excess Gibbs free energy GE in binary systems.a

x1 y1 p/kPa c1 c2 GE/(J  mol1)

{2-Propanol (1) + 2,2,4-trimethylpentane (2)}
T = 330.00 K
0.0000 0.0000 25.47 10.768 1.000 0.0
0.0066 0.1004 28.17 9.924 1.000 56.5
0.0259 0.2692 34.15 7.898 1.006 217.4
0.0797 0.3897 39.82 5.600 1.028 467.1
0.1739 0.4458 43.20 3.788 1.083 758.0
0.2737 0.4834 44.96 2.541 1.203 1044.7
0.3859 0.5189 45.93 1.860 1.395 1217.0
0.4952 0.5459 46.36 1.525 1.630 1249.7
0.6050 0.5701 46.36 1.315 1.954 1180.8
0.7036 0.6005 45.95 1.183 2.388 1033.9
0.7922 0.6336 44.96 1.096 2.991 829.1
0.8649 0.6921 43.21 1.043 3.801 595.0
0.8665 0.6944 43.14 1.042 3.832 587.0
0.9051 0.7387 41.58 1.022 4.441 441.9
0.9365 0.7871 39.73 1.010 5.086 309.4
0.9586 0.8465 37.79 1.004 5.714 197.2
0.9754 0.8953 36.08 1.001 6.232 114.7
0.9883 0.9397 34.63 1.000 6.652 53.4
0.9958 0.9799 33.62 1.000 6.939 13.9
1.0000 1.0000 33.25 1.000 7.043 0.0
T = 340.00 K
0.0000 0.0000 36.64 9.590 1.000 0.0
0.0080 0.1065 40.57 8.877 1.000 56.7
0.0873 0.3920 57.92 5.229 1.026 457.9
0.1646 0.4641 63.75 3.570 1.080 755.9
0.2636 0.5048 66.79 2.495 1.186 1024.8
0.3782 0.5358 68.63 1.844 1.364 1202.0
0.4823 0.5642 69.53 1.530 1.573 1241.9
0.5955 0.5963 69.84 1.316 1.877 1181.8
0.6949 0.6224 69.52 1.187 2.262 1046.6
0.7882 0.6624 68.43 1.100 2.795 850.6
0.8565 0.7128 66.18 1.045 3.531 614.7
0.8626 0.7128 66.29 1.046 3.503 622.7
0.8960 0.7543 64.22 1.024 4.068 468.9
0.9299 0.7998 61.85 1.012 4.645 333.2
0.9510 0.8537 59.36 1.005 5.201 218.6
0.9721 0.9054 56.97 1.002 5.700 126.8
0.9860 0.9498 54.95 1.000 6.100 59.5
0.9956 0.9804 53.46 1.000 6.385 14.6
1.0000 1.0000 52.97 1.000 6.480 0.0

{2-Propanol (1) + 2,4-dimethyl-3-pentanone (2)}

T = 330.00 K
0.0000 0.0000 8.87 2.755 1.000 0.0
0.0363 0.2130 11.38 2.475 1.002 89.2
0.0737 0.3567 13.40 2.248 1.007 169.7
0.1305 0.4889 15.93 1.975 1.021 278.1
0.1977 0.5856 18.42 1.726 1.047 387.4
0.2727 0.6540 20.71 1.524 1.086 479.3
0.3531 0.7085 22.72 1.374 1.139 540.2
0.4267 0.7453 24.38 1.270 1.199 567.0
0.5010 0.7804 25.75 1.198 1.264 567.3
0.5961 0.8157 27.34 1.129 1.361 537.0
0.6728 0.8467 28.57 1.085 1.461 486.6
0.7213 0.8648 29.34 1.061 1.537 441.5
0.7984 0.8949 30.46 1.033 1.676 354.2
0.8587 0.9234 31.30 1.017 1.808 270.4
0.9084 0.9474 31.94 1.008 1.935 193.4
0.9455 0.9667 32.40 1.004 2.044 129.7
0.9728 0.9828 32.72 1.001 2.132 80.2
0.9894 0.9940 32.93 1.000 2.194 46.8
1.0000 1.0000 33.25 1.000 2.284 0.0
T = 340.00 K
0.0000 0.0000 13.55 2.634 1.000 0.0
0.0370 0.2173 17.44 2.377 1.002 89.7
0.0767 0.3634 20.55 2.173 1.007 168.9
0.1348 0.4987 24.44 1.927 1.020 274.0
0.2007 0.5928 28.28 1.702 1.043 379.1
0.2759 0.6579 31.92 1.513 1.080 470.3
0.3531 0.7137 35.06 1.373 1.127 531.3
0.4307 0.7545 37.80 1.270 1.183 561.5

(continued on next page)

86 J. Pavlcek, I. Wichterle / J. Chem. Thermodynamics 45 (2012) 8389

TABLE 3 (continued)

x1 y1 p/kPa c1 c2 GE/(J  mol1)

0.5003 0.7839 39.98 1.201 1.242 565.1
0.5915 0.8233 42.66 1.130 1.335 538.7
0.6729 0.8518 44.72 1.086 1.428 491.3
0.7221 0.8704 46.04 1.063 1.501 447.0
0.7941 0.9016 47.90 1.035 1.627 364.6
0.8570 0.9274 49.42 1.018 1.757 278.0
0.9076 0.9509 50.59 1.008 1.880 197.8
0.9452 0.9694 51.43 1.004 1.984 133.0
0.9726 0.9844 52.07 1.001 2.074 78.9
0.9905 0.9935 52.43 1.000 2.131 45.9
1.0000 1.0000 52.97 1.000 2.213 0.0

{2,2,4-trimethylpentane (1) + 2,4-dimethyl-3-pentanone (2)}

T = 330.00 K
0.0000 0.0000 8.87 2.359 1.000 0.0
0.0418 0.1743 10.74 2.087 1.003 89.8
0.0698 0.2607 11.72 1.949 1.007 141.4
0.1051 0.3476 12.72 1.814 1.013 196.6
0.1459 0.4260 13.80 1.680 1.024 255.7
0.1971 0.5004 14.97 1.552 1.040 316.9
0.2400 0.5441 15.93 1.460 1.057 362.3
0.2525 0.5613 16.27 1.430 1.065 377.0
0.3103 0.6153 17.32 1.345 1.091 417.2
0.3223 0.6220 17.61 1.325 1.098 425.9
0.3898 0.6793 18.71 1.251 1.134 452.8
0.4147 0.6877 19.17 1.225 1.151 459.3
0.4759 0.7293 20.00 1.180 1.188 463.6
0.5228 0.7479 20.71 1.146 1.225 458.5
0.6296 0.8019 21.99 1.091 1.313 423.2
0.7236 0.8472 23.02 1.054 1.417 362.8
0.8127 0.8893 23.87 1.028 1.545 281.9
0.8858 0.9278 24.51 1.012 1.686 195.6
0.9423 0.9610 24.96 1.004 1.829 113.6
0.9804 0.9860 25.25 1.001 1.953 49.0
1.0000 1.0000 25.47 1.000 2.053 0.0
T = 340.00 K
0.0000 0.0000 13.55 2.311 1.000 0.0
0.0472 0.1752 16.31 2.039 1.003 97.0
0.0776 0.2598 17.90 1.891 1.008 157.1
0.1149 0.3444 19.28 1.767 1.015 211.9
0.1569 0.4218 20.74 1.647 1.025 268.9
0.2079 0.4917 22.33 1.529 1.041 328.0
0.2500 0.5369 23.64 1.444 1.058 372.2
0.2631 0.5574 24.14 1.413 1.066 387.8
0.3206 0.6113 25.56 1.334 1.091 426.2
0.3335 0.6142 25.87 1.319 1.097 433.1
0.4000 0.6705 27.44 1.246 1.133 460.6
0.4282 0.6809 28.09 1.219 1.151 467.1
0.4845 0.7217 29.13 1.179 1.184 471.1
0.5312 0.7403 30.12 1.145 1.220 466.2
0.6350 0.7947 31.86 1.092 1.305 431.9
0.7306 0.8429 33.32 1.053 1.409 369.7
0.8163 0.8874 34.49 1.027 1.533 288.0
0.8879 0.9258 35.33 1.012 1.665 202.6
0.9422 0.9602 35.95 1.004 1.803 119.3
0.9792 0.9859 36.33 1.001 1.918 55.1
1.0000 1.0000 36.64 1.000 2.023 0.0
a
Standard uncertainties u are u(x) = u(y) = 0.0005, u(T) = 0.01 K and u(p) = 0.01 kPa.

to the experimental value of vapour pressure at the particular tem-
perature. Naturally, this is not applicable to the new procedure
[18], and to keep the experimental pressures unchanged for pure
components, the measured vapour pressures of pure component
were used for functional correlation of Antoine parameters for this
purpose only.
The standard deviations necessary for computation input were
estimated as 0.0030 for mole fraction of phases, 0.01 K for tempera-
ture and 0.01 kPa for pressure. Parameters for the Wilson and NRTL
equations are presented in tables 4 and 5, respectively, together with
resulting standard deviations for all variables (x, y, p, T). The approx-
imate values of molar volumes of pure components required for the
Wilson equation are given in table 4, however, they have always
been evaluated at the temperature iterated during computation.
The experimental data are illustrated in gures 1 to 3 as xyp plots.
Solid lines represent the smoothed values based on optimised NRTL
equation parameters. There are the literature data for the (2-propa-
nol + 2,2,4-trimethylpentane) system [1] measured exactly at the
same isotherms. For comparison they are plotted together with
newly re-measured data; a good agreement is obvious (see discus-
sion). For qualitative comparison, the data [25] determined at
348.15 K are also plotted in gure 1.
The experimental data for the ternary system were determined
at the identical isothermal conditions as the binary systems and
are presented in table 6. Overall compositions of mixtures in the
equilibrium still were formed approximately by subsequent addi-
 J. Pavlcek, I. Wichterle / J. Chem. Thermodynamics 45 (2012) 8389 87

TABLE 4
Parameters of the Wilson equation valid between (330.00 and 340.00) K, and evaluated standard deviations.

k12  k11/(J  mol1) k21  k22/(J  mol1) V1/(ml  mol1) V2/(ml  mol1) No. of points Dx Dy Dp/kPa DT/K
{2-Propanol (1) + 2,2,4-trimethylpentane (2)}
6347.47 958.539 88.489.6 172.7174.9 35 0.0101 0.0065 0.016 0.037
{2-Propanol (1) + 2,4-dimethyl-3-pentanone (2)}
3168.00 566.172 88.489.6 148.2149.9 34 0.0074 0.0106 0.008 0.008
{2,2,4-Trimethylpentane (1) + 2,4-dimethyl-3-pentanone (2)}
886.448 1201.37 172.7174.9 148.2149.9 38 0.0059 0.0127 0.011 0.007

TABLE 5
Parameters of the NRTL equation valid between (330.00 and 340.00) K, and evaluated standard deviations.

g12  g22/(J  mol1) g21  g11/(J  mol1) aij No. of points Dx Dy Dp/kPa DT/K
{2-Propanol (1) + 2,2,4-trimethylpentane (2)}
1973.53 1608.54 1.2678 35 0.0051 0.0060 0.003 0.006
{2-Propanol (1) + 2,4-dimethyl-3-pentanone (2)}
993.709 743.414 1.9817 34 0.0072 0.0094 0.007 0.008
{2,2,4-Trimethylpentane (1) + 2,4-dimethyl-3-pentanone (2)}
1277.63 1702.42 1.4421 38 0.0062 0.0109 0.010 0.010

100 60

90
50

80

40
70
p/kPa

p/kPa

60 30

50
20

40

10
30

20 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
x1, y1 x1, y1

FIGURE 1. Isothermal (vapour + liquid) equilibrium in the {2-propanol (1) + 2,2,4-
trimethylpentane (2)} system (x1y1p plot). Experimental data: 330.00 K (d, s),
340.00 K (j, h), 348.15 K (N, 4) [25]; solid points liquid phase, open points
vapour phase; () NRTL correlation; x1 and y1 denotes mole fraction of component
1 in liquid and vapour phase, respectively. The data [1] measured at the same
temperatures (marked as  and ) are plotted for comparison.
FIGURE 2. Isothermal (vapour + liquid) equilibrium in the {2-propanol (1) + 2,4-
dimethyl-3-pentanone (2)} system (x1y1p plot). Experimental data: 330.00 K
(d, s), 340.00 K (j, h); solid points liquid phase, open points vapour phase; ()
NRTL correlation; x1 and y1 denotes mole fraction of component 1 in liquid and
vapour phase, respectively.

where Aij = (Vj/Vi)exp[(kij  kii)/RT], and

tion of 2-propanol to several initial (2,2,4-trimethylpentane + 2,4- P3 P3 !
X3
dimethyl-3-pentanone) mixtures; then, the region of ternary com- r1 sri Gri xr xr Gir str Gtr xt
ln ci P 3
P3 sir  Pt13 ; 4
positions was regularly covered. Altogether 64 experimental points s1 G si x s r1 s1 Gsr xs s1 Gsr xs
were determined.
The parameters obtained from the correlation of the three bin- where Gij = exp[aijsij]; sij = (gij  gjj)/RT; sii = 0; aij = aji; Gii = 1,
ary VLE data were exploited for prediction of ternary data using respectively. The necessary molar volumes were estimated with
both the Wilson and NRTL equations expressing the activity coef- use of the method of Hougen and Watson [16].
cient, ci (i = 1, 2, 3) as The computation was carried out by means of the method pub-
! lished in [17] enabling the calculation of the closest solution by
X
3 X
3
xr Ari minimisation of standard deviations of all involved variables (tem-
ln ct  ln xs Ais 1 P3 ; 3 perature, pressure, and vapour and liquid compositions). Resulting
s1 r1 s1 xs Ars
absolute deviations are averaged and summarised in table 7.
88 J. Pavlcek, I. Wichterle / J. Chem. Thermodynamics 45 (2012) 8389

40 TABLE 6
(Vapour + liquid) equilibrium experimental data in the ternary {2-propanol
(1) + 2,2,4-trimethylpentane (2) + 2,4-dimethyl-3-pentanone (3)} system.a

x1 x2 y1 y2 p/kPa
T = 330.00 K
30 0.0174 0.4234 0.0830 0.6524 20.78
0.0521 0.4029 0.2016 0.5687 23.44
0.1085 0.3691 0.3279 0.4839 26.74
0.1905 0.3260 0.4232 0.4197 29.96
0.2821 0.2740 0.4293 0.3699 31.97
0.3824 0.2199 0.5494 0.3273 33.33
p/kPa

0.4759 0.1676 0.6011 0.2823 33.93

20
0.5708 0.1246 0.6528 0.2410 34.31
0.6532 0.0899 0.7012 0.2025 34.05
0.7257 0.0621 0.7510 0.1629 33.76
0.7859 0.0424 0.7969 0.1268 33.36
0.0102 0.8388 0.0888 0.8296 24.95
0.0374 0.8143 0.2386 0.6969 29.25
10 0.0905 0.7657 0.3499 0.5983 33.80
0.1799 0.6900 0.4315 0.5270 36.48
0.2820 0.5975 0.4778 0.4865 38.24
0.3898 0.4998 0.5131 0.4553 39.37
0.5021 0.4005 0.5461 0.4254 39.81
0.6059 0.3072 0.5805 0.3931 40.73
0 0.6993 0.2271 0.6148 0.3613 40.11
0.0 0.2 0.4 0.6 0.8 1.0 0.7744 0.1646 0.6564 0.3217 39.29
x1, y1 0.8382 0.1123 0.7057 0.2746 38.17
0.0148 0.0572 0.0820 0.2120 10.64
0.0423 0.0538 0.2131 0.1799 12.73
FIGURE 3. Isothermal (vapour + liquid) equilibrium in the {2,2,4-trimethylpentane
0.0863 0.0492 0.3497 0.1446 14.76
(1) + 2,4-dimethyl-3-pentanone (2)} system (x1y1p plot). Experimental data:
0.1594 0.0393 0.4946 0.1043 17.45
330.00 K (d, s), 340.00 K (j, h); solid points liquid phase, open points vapour
0.2486 0.0305 0.5976 0.0781 19.89
phase () NRTL correlation; x1 and y1 denotes mole fraction of component 1 in
0.3426 0.0228 0.6675 0.0573 21.80
liquid and vapour phase, respectively.
0.4258 0.0162 0.7205 0.0421 23.23
0.5189 0.0114 0.7696 0.0314 24.73
0.6096 0.0078 0.8073 0.0230 25.92
4. Discussion and conclusions 0.6889 0.0053 0.8398 0.0168 26.91
T = 340.00 K
Vapour pressure of pure 2,4-dimethyl-3-pentanone was deter- 0.0177 0.4313 0.0832 0.6406 30.51
mined by Dreisbach and Shrader [19] but the substance used for 0.0514 0.4103 0.2089 0.5572 34.36
measurement was not sufciently pure (mass fraction equal to 0.1083 0.3760 0.3340 0.4720 39.23
0.9894). Therefore, a little shift can be observed between present 0.1898 0.3326 0.4373 0.4046 44.47
0.2765 0.2797 0.5056 0.3530 47.79
and published [19] data set in the log p versus 1/T diagram. It is be-
0.3763 0.2262 0.5664 0.3097 50.13
lieved that our measurements are more reliable due to the better 0.4711 0.1750 0.6208 0.2634 51.48
purity of the compound. 0.5649 0.1303 0.6690 0.2237 52.51
No published (vapour + liquid) equilibrium data for the studied 0.6479 0.0941 0.7175 0.1900 52.43
0.7212 0.0642 0.7640 0.1532 52.39
systems were found in the bibliography covering the period 1888
0.7827 0.0432 0.8073 0.1198 52.08
2007 [20] except for the (2-propanol + 2,2,4-trimethylpentane) 0.0109 0.8382 0.0953 0.8220 36.19
system. Nevertheless, the two isobaric data sets found [21,22] can- 0.0252 0.8215 0.2395 0.6937 42.41
not be used for comparison. The isothermal data were measured at 0.0935 0.7662 0.3591 0.5869 49.37
298.15 K [23], at 318.10 K [24], and at 348.15 K [25]. The older data 0.1817 0.6905 0.4440 0.5137 53.95
0.2716 0.6071 0.4995 0.4647 56.96
measured exactly at the same isotherms, namely at (330.00 and
0.3803 0.5075 0.5387 0.4299 58.81
340.00) K [1], and the data [25] are plotted for comparison in gure 0.4935 0.4079 0.5075 0.4013 60.01
1 together with the present data; a good agreement is evident, too. 0.5973 0.3153 0.6041 0.3702 62.00
The new measurements of VLE data for this system were carried 0.6902 0.2361 0.6411 0.3354 61.16
0.7692 0.1701 0.6853 0.2934 60.20
out in order to prove the mutual compatibility with [1].
0.8296 0.1209 0.7319 0.2491 58.78
The quantitative comparison of the (2-propanol + 2,2,4-trim- 0.0165 0.0625 0.0896 0.2115 17.33
ethylpentane) data with all published isothermal data, namely 0.0430 0.0571 0.2180 0.1760 19.46
with data from [1,2325], was achieved by processing of those data 0.0910 0.0530 0.3605 0.1434 22.58
with use of the evaluated NRTL parameters from table 5. Computa- 0.1643 0.0422 0.5021 0.1017 26.67
0.2502 0.0328 0.6061 0.0746 30.50
tion was carried out for this binary system in the same way as for
0.3404 0.0239 0.6754 0.0546 33.57
the ternary system (see above); results are presented in table 8. It 0.4282 0.0172 0.7291 0.0402 35.99
is necessary to point out, that despite the new NRTL parameters 0.5200 0.0122 0.7744 0.0298 38.46
were evaluated only for the narrow temperature range (330.00 to 0.6065 0.0084 0.8142 0.0216 40.50
340.00) K, the excellent prediction was found even for isotherms 0.6858 0.0056 0.8479 0.0159 42.18

quite far out of this range. This is an undisputable proof of excel- a

Standard uncertainties u are u(x) = u(y) = 0.0005, u(T) = 0.01 K, and
lent quality of data. u(p) = 0.01 kPa.
Azeotropic behaviour was found in the (2-propanol + 2,2,4-
trimethylpentane) system. Experimental data for azeotropes were
obtained by plotting x versus xy and x versus p; numerically and xaz = 0.5998, paz = 69.87 kPa for (330.00 and 340.00) K, respec-
smoothed curves in these simple plots yielded azeotropic compo- tively. Such procedure is more reliable than the evaluation via VLE
sition xaz and pressure paz, namely xaz = 0.5632, paz = 46.41 kPa, correlation equation. Both the new and published [1,13,2125]
 J. Pavlcek, I. Wichterle / J. Chem. Thermodynamics 45 (2012) 8389 89

TABLE 7
Prediction of (vapour + liquid) equilibrium in the {2-propanol (1) + 2,2,4-trimethylpentane (2) + 2,4-dimethyl-3-pentanone (3)} system at (330.00 and 340.00) K using the binary
parameters of the Wilson and NRTL equations.

T/K Dx 1 Dx2 Dx3 Dx Dy 1 Dy2 Dy3 Dy Dp/kPa DT/K

Wilson equation
330.00 0.0172 0.0112 0.0271 0.0185 0.0132 0.0160 0.0181 0.0158 0.02 0.28
340.00 0.0216 0.0122 0.0329 0.0222 0.0135 0.0153 0.0186 0.0158 0.03 0.30
Mean 0.0194 0.0117 0.0299 0.0203 0.0134 0.0157 0.0184 0.0158 0.03 0.28
NRTL equation
330.00 0.0185 0.0116 0.0286 0.0196 0.0157 0.0171 0.0193 0.0174 0.02 0.29
340.00 0.0204 0.0112 0.0302 0.0206 0.0161 0.0158 0.0191 0.0170 0.03 0.27
Mean 0.0195 0.0114 0.0294 0.0201 0.0159 0.0164 0.0192 0.0172 0.02 0.28

D is an absolute average deviation of calculated and experimental data.

TABLE 8 are very good. It should be pointed out that these results need not
Comparison of published isothermal data on (vapour + liquid) equilibrium in the {2- necessarily reect the quality of data. The experimental data are
propanol (1) + 2,2,4-trimethylpentane (2)} binary system with the data calculated
most likely better, because the imperfections of models also con-
using the binary parameters of the NRTL equation (from table 5).
tribute to certain worsening of calculated values.
T/K Dx1 Dy1 Dp/kPa DT/K Reference
298.15 0.0095 0.0150 0.01 0.65 [23]
Acknowledgements
318.10 0.0065 0.0070 0.01 0.13 [24]
330.00 0.0028 0.0017 0.01 0.05 [1]
330.00 0.0051 0.0060 0.00 0.01 This work The authors acknowledge the technical assistance of Mr. .
340.00 0.0031 0.0037 0.01 0.07 [1] Psutka and a partial support of the Grant Agency of the Czech
340.00 0.0051 0.0060 0.00 0.01 This work Republic (Grant No. 104/07/0444).
348.15 0.0027 0.0032 0.01 0.05 [25]

D is an absolute average deviation of calculated and experimental data.

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