Fluid Phase Equilibria 209 (2003) 8194

(P, V, T, x) Measurements of the system benzene

+ 1,3,5-trimethylbenzene at temperatures from
298.15 to 328.15 K and at pressures up to 40 MPa
L. Morvkov, Z. Wagner, J. Linek
E. Hla Laboratory of Thermodynamics, Institute of Chemical Process Fundamentals,
Academy of Sciences of the Czech Republic, 165 02 Prague 6, Czech Republic
Received 29 November 2002; accepted 5 March 2003

Abstract
Densities were measured for the liquid benzene and 1,3,5-trimethylbenzene, and for nine of their mixtures at four
temperatures between 298.15 and 328.15 K and at pressures up to 40 MPa. An apparatus for density measurements
of liquids and liquid mixtures whose main part is a high-pressure vibrating-tube densimeter working in a static mode
was used for the measurement. The density data were fitted to the Tait equation and the isothermal compressibilities
were calculated with the aid of this equation. Excess molar volumes were also calculated from the densities and
fitted to the RedlichKister equation.
2003 Elsevier Science B.V. All rights reserved.
Keywords: 1,3,5-Trimethylbenzene; Benzene; RedlichKister equation

1. Introduction
Research activities of our laboratory comprise, among others, the systematic measurement of volumetric properties of different groups of organic compounds. Recently, we have measured densities and
determined excess volumes at elevated temperatures and moderately high pressures of the alkane +
1-chloroalkane mixtures [17] with the aim to prepare a database for testing theories of the liquid state
(equations of state). Our new project is devoted to the systematic study of liquid systems containing
aromatics with respect to their environmental importance.
To our knowledge [8], there exist no volumetric data for the liquid phase of the system benzene +
1,3,5-trimethylbenzene (mesitylene) at elevated pressures. Therefore, we have measured densities and
calculated isothermal compressibilities and excess volumes of the system. The apparatus based on a

Corresponding author. Tel.: +420-2-20370270/96780270; fax: +420-2-20920661.

E-mail address: linek@icpf.cas.cz (J. Linek).
0378-3812/03/$ see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0378-3812(03)00079-7

82

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

high-pressure vibrating-tube densimeter working in a static mode [2] and designed for measuring the
pVT behaviour of pure liquids and liquid mixtures at elevated temperatures (283333 K) and moderately
high pressures (40 MPa) was used for the measurements. The measurements were carried out at the
temperatures 298.15, 308.15, 318.15, and 328.15 K and in the pressure range 0.140 MPa.
2. Experimental
2.1. Materials
The benzene (Fluka-RdH, A.R., g.c. mass fraction >0.997) and 1,3,5-trimethylbenzene (Fluka, puriss.,
g.c. mass fraction 0.99) were used without further purification. Both substances were dried and stored
over 0.4 nm molecular sieves. In order to check the purity of the compounds, their densities and refractive
indices were determined at T = 298.15 K and compared with literature values [911]. The agreement was
found, in general, to be good (Table 1). The purity of the chemicals was checked by gas chromatography
(HP Series II model 5890 chromatograph with capillary column type 1909 1Z-413E and f.i.d., column
temperature 413.3 K, helium flow rate 4.2 104 cm3 s1 ).
2.2. Apparatus and procedure
A schematic diagram and detailed description of the apparatus used for the measurement was given in
our previous work [2]. It consists mainly of the measuring cell DMA 512P, supplied by Anton Paar, Graz,
Austria. The temperature of the measuring cell was controlled by a thermostat LAUDA RC 20 CP (Lauda,
Koenigshofen, Germany). The thermostat maintained the temperature in the measuring cell under control
within 0.01 K. The pressure was measured with a pressure transducer LPN-N having a voltage output
(ECOM, Prague, Czech Republic). The pressure gauge was calibrated with a Ruska pressure calibration
system (Ruska Instruments Co., Houston, TX, USA). The accuracy of the pressure measurement is better
than 0.1 MPa. The pressure in the measuring cell can be set by means of the manual pressure controller
accurate to 0.01 MPa. The DMA 512P measuring cell is connected to the DMA 58 densimeter which serves
as a frequency counter and evaluates the oscillating period from the signals of the measuring cell filled with
sample. The samples of measured liquid mixtures prepared by weight in special vessels [3] are moved into
the measuring cell with a liquid chromatography pump LCP 4000.1 (ECOM, Prague, Czech Republic).
The sample density was deduced from the period of vibration of the vibrating-tube densimeter as
follows:
(T, p) = a(T, p) 2 + b(T, p).

(1)

Table 1
Densities and refractive index values nD at T = 298.15 K of the pure components, and their comparison with literature
Component

Benzene
1,3,5-Trimethylbenzene

(g cm3 )

nD

Experimental

Literature

Reference

Experimental

Literature

Reference

0.87362
0.86114

0.8737
0.86111

[911]
[911]

1.4979
1.4967

1.49792
1.49684

[911]
[911]

w is the mass fraction purity as determined by g.l.c.

0.9996
0.9927

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

83

The coefficients a(T, p) and b(T, p) are two characteristic temperature and pressure dependent parameters
of the apparatus, which have to be determined by measuring the periods 1 and 2 for two substances of
known density of the T, p set considered. For calibration (at ambient temperature and pressure), water
and air are usually used as standards. For very accurate measurements, especially at higher temperatures
and pressures, a pair of fluids with accurately determined densities is recommended. The density of a
sample is then calculated from Eq. (1) with the parameters determined by calibration.
The choice of standards of known density at high pressures and temperatures is rather limited. The
manufacturer of the densimeter DMA 512P recommends the following substances: nitrogen, benzene,
pentane, dichloromethane and water. In our case, the apparatus was calibrated [2] with bidistilled water
and heptane. The density data used for the calibration were taken from [12] for water and from [13] for
heptane.
The samples for the density measurements were prepared by weight (SCALTEC SBC 21 balance
with an accuracy of 1 105 g) for the whole mole fraction range and then partially degassed in
tightly closed special vessels of negligible vapour space [3] at the maximum measurement temperature
for 3 h by means of an ultrasonic thermostatted bath (Bandelin RK 100H, Berlin, Germany) prior to
determining their density in order to prevent the formation of bubbles in the densimeter. To estimate the
effect of evaporation on the sample composition, the calculations were carried out taking into account
the vapourliquid equilibrium of the given system at the conditions applied. The concentration changes
are proved to be well below the stated accuracy in composition.
The experimental uncertainty in the mole fraction composition is less than 5 105 , and that in the
density is approximately 1 104 g cm3 .
3. Results and discussion
3.1. Densities
The results of the density measurements are given in Table 2. Densities of the pure substances and of
nine weighed mixtures were measured at 23 pressures over the range 0.1 to nearly 40 MPa.
The isothermal densities of pure substances and their mixtures at a given composition were fitted to
the Tait equation



0
D+p
,
(2)
= C ln
D + p0

where 0 is the density at a reference pressure p0 (p0 = 0.101325 MPa in this work). The values of
0 were those [8] obtained by measuring the liquid samples with a low-pressure DMA 58 densimeter
because the high-pressure equipment cannot in principle provide sufficiently accurate data at atmospheric
pressure. Since the procedure for the parameters determination requires a special approach, it is described
a little more in detail.
Values of parameters C and D were determined by minimisation of the following objective function:

n


i,calc i,exp 2
S=
,
(3)
i,exp
i=1
where n is the number of data points.

84

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

Table 2
Experimental values of density and calculated isothermal compressibility T for x benzene + (1x) 1,3,5-trimethylbenzene
at pressure p and temperature T
x

p (MPa)

T = 298.15 K

T = 308.15 K

(g cm3 )

104 T
(MPa1 )

(g cm3 )

T = 318.15 K

104 T
(MPa1 )

(g cm3 )

T = 328.15 K

104 T
(MPa1 )

(g cm3 )

104 T
(MPa1 )

0.00000

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.86104
0.86236
0.86375
0.86511
0.86645
0.86778
0.86845
0.86912
0.87040
0.87166
0.87292
0.87415
0.87536
0.87655
0.87774
0.87889
0.87947
0.88007
0.88120
0.88231
0.88342
0.88452
0.88503

7.92
7.80
7.69
7.58
7.47
7.36
7.31
7.26
7.16
7.07
6.97
6.88
6.79
6.71
6.62
6.54
6.50
6.46
6.38
6.31
6.24
6.16
6.13

0.85292
0.85439
0.85583
0.85728
0.85868
0.86010
0.86078
0.86146
0.86278
0.86412
0.86545
0.86673
0.86802
0.86926
0.87050
0.87171
0.87229
0.87292
0.87410
0.87528
0.87643
0.87757
0.87812

8.68
8.51
8.36
8.20
8.06
7.92
7.85
7.78
7.65
7.53
7.41
7.29
7.17
7.06
6.96
6.86
6.80
6.76
6.66
6.56
6.47
6.38
6.34

0.84472
0.84630
0.84781
0.84931
0.85081
0.85226
0.85299
0.85369
0.85511
0.85652
0.85791
0.85924
0.86060
0.86195
0.86322
0.86449
0.86510
0.86574
0.86699
0.86823
0.86939
0.87059
0.87117

9.14
8.97
8.81
8.65
8.50
8.36
8.29
8.22
8.08
7.95
7.82
7.70
7.59
7.47
7.36
7.25
7.20
7.15
7.05
6.95
6.86
6.76
6.72

0.83640
0.83816
0.83976
0.84134
0.84292
0.84443
0.84520
0.84597
0.84744
0.84892
0.85038
0.85179
0.85317
0.85456
0.85592
0.85725
0.85791
0.85856
0.85988
0.86113
0.86238
0.86363
0.86423

9.61
9.44
9.27
9.11
8.95
8.80
8.73
8.66
8.52
8.39
8.25
8.13
8.01
7.89
7.77
7.66
7.61
7.56
7.45
7.35
7.25
7.15
7.11

0.10849

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55

0.86088
0.86223
0.86364
0.86507
0.86642
0.86778
0.86845
0.86911
0.87045
0.87174
0.87302
0.87428
0.87553
0.87676
0.87797
0.87919
0.87976
0.88035
0.88152
0.88265

8.39
8.24
8.09
7.95
7.81
7.68
7.61
7.55
7.42
7.30
7.19
7.08
6.97
6.86
6.76
6.66
6.61
6.57
6.47
6.38

0.85217
0.85363
0.85511
0.85656
0.85799
0.85943
0.86009
0.86079
0.86217
0.86351
0.86485
0.86616
0.86744
0.86871
0.86999
0.87123
0.87184
0.87244
0.87362
0.87480

8.48
8.35
8.23
8.11
7.99
7.88
7.82
7.77
7.66
7.55
7.45
7.36
7.26
7.17
7.08
6.99
6.94
6.90
6.82
6.74

0.84393
0.84554
0.84710
0.84864
0.85013
0.85163
0.85235
0.85309
0.85453
0.85595
0.85734
0.85872
0.86009
0.86140
0.86272
0.86405
0.86467
0.86530
0.86658
0.86782

9.12
8.97
8.82
8.68
8.54
8.41
8.35
8.29
8.16
8.04
7.93
7.82
7.71
7.60
7.50
7.40
7.35
7.30
7.21
7.12

0.83554
0.83733
0.83897
0.84057
0.84218
0.84373
0.84452
0.84528
0.84680
0.84829
0.84977
0.85120
0.85262
0.85402
0.85541
0.85678
0.85745
0.85811
0.85945
0.86072

9.72
9.55
9.38
9.23
9.08
8.93
8.86
8.79
8.65
8.52
8.39
8.27
8.15
8.03
7.92
7.81
7.75
7.70
7.60
7.50

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

85

Table 2 (Continued )
x

p (MPa)

T = 298.15 K

T = 308.15 K

T = 318.15 K

T = 328.15 K

(g cm3 )

10 T
(MPa1 )

(g cm3 )

36.58
38.60
39.62

0.88379
0.88490
0.88547

6.29
6.21
6.17

0.87597
0.87712
0.87769

6.66
6.58
6.54

0.86903
0.87024
0.87086

7.03
6.94
6.90

0.86199
0.86325
0.86389

7.40
7.30
7.26

0.19391

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.86068
0.86204
0.86347
0.86489
0.86627
0.86765
0.86834
0.86901
0.87036
0.87166
0.87294
0.87422
0.87550
0.87674
0.87796
0.87917
0.87977
0.88036
0.88156
0.88270
0.88385
0.88498
0.88552

8.39
8.24
8.10
7.97
7.84
7.72
7.65
7.59
7.48
7.36
7.25
7.15
7.04
6.94
6.85
6.75
6.71
6.66
6.57
6.49
6.40
6.32
6.28

0.85189
0.85340
0.85491
0.85636
0.85780
0.85920
0.85992
0.86061
0.86200
0.86337
0.86470
0.86603
0.86734
0.86863
0.86992
0.87119
0.87180
0.87240
0.87362
0.87482
0.87599
0.87717
0.87774

8.59
8.45
8.33
8.20
8.08
7.97
7.91
7.85
7.74
7.64
7.53
7.43
7.34
7.24
7.15
7.06
7.01
6.97
6.89
6.80
6.72
6.64
6.60

0.84350
0.84514
0.84674
0.84829
0.84982
0.85131
0.85206
0.85281
0.85427
0.85570
0.85711
0.85851
0.85989
0.86126
0.86258
0.86389
0.86455
0.86520
0.86648
0.86772
0.86894
0.87016
0.87078

9.23
9.07
8.93
8.78
8.65
8.51
8.45
8.38
8.26
8.14
8.02
7.91
7.80
7.69
7.59
7.49
7.44
7.39
7.29
7.20
7.11
7.02
6.98

0.83501
0.83677
0.83844
0.84008
0.84172
0.84330
0.84408
0.84486
0.84640
0.84792
0.84941
0.85087
0.85231
0.85374
0.85514
0.85653
0.85721
0.85788
0.85922
0.86051
0.86179
0.86305
0.86369

9.84
9.67
9.50
9.34
9.18
9.03
8.96
8.89
8.75
8.61
8.48
8.36
8.23
8.11
8.00
7.89
7.83
7.78
7.67
7.57
7.47
7.37
7.33

0.29799

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50

0.86067
0.86206
0.86352
0.86495
0.86636
0.86774
0.86840
0.86911
0.87046
0.87178
0.87309
0.87439
0.87563
0.87689
0.87813
0.87934
0.87995
0.88055

8.44
8.30
8.16
8.02
7.89
7.76
7.70
7.64
7.52
7.41
7.30
7.19
7.09
6.99
6.89
6.80
6.75
6.70

0.85197
0.85350
0.85504
0.85654
0.85802
0.85947
0.86018
0.86089
0.86231
0.86369
0.86507
0.86641
0.86774
0.86905
0.87035
0.87164
0.87226
0.87287

9.00
8.84
8.68
8.53
8.38
8.24
8.17
8.11
7.97
7.85
7.72
7.60
7.49
7.38
7.27
7.16
7.11
7.06

0.84340
0.84506
0.84667
0.84825
0.84981
0.85134
0.85209
0.85284
0.85433
0.85579
0.85723
0.85864
0.86002
0.86140
0.86275
0.86409
0.86474
0.86540

9.59
9.41
9.23
9.07
8.90
8.75
8.67
8.60
8.45
8.31
8.18
8.05
7.92
7.80
7.68
7.57
7.51
7.46

0.83488
0.83670
0.83841
0.84008
0.84173
0.84335
0.84415
0.84494
0.84652
0.84805
0.84955
0.85105
0.85252
0.85396
0.85539
0.85680
0.85748
0.85818

10.40
10.20
10.00
9.79
9.59
9.40
9.31
9.22
9.05
8.88
8.72
8.56
8.41
8.27
8.13
7.99
7.93
7.86

10 T
(MPa1 )
4

(g cm3 )

10 T
(MPa1 )
4

(g cm3 )

104 T
(MPa1 )

86

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

Table 2 (Continued )
x

p (MPa)

T = 298.15 K

T = 308.15 K

T = 318.15 K

T = 328.15 K

(g cm3 )

10 T
(MPa1 )

(g cm3 )

32.53
34.55
36.58
38.60
39.62

0.88172
0.88287
0.88404
0.88516
0.88575

6.61
6.53
6.44
6.36
6.32

0.87411
0.87533
0.87652
0.87771
0.87829

6.96
6.87
6.77
6.68
6.64

0.86671
0.86798
0.86922
0.87046
0.87108

7.35
7.25
7.15
7.05
7.00

0.85954
0.86087
0.86217
0.86346
0.86411

7.74
7.62
7.50
7.39
7.33

0.4346

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.86111
0.86253
0.86401
0.86549
0.86694
0.86833
0.86902
0.86973
0.87112
0.87245
0.87377
0.87509
0.87637
0.87769
0.87892
0.88017
0.88077
0.88139
0.88258
0.88378
0.88495
0.88612
0.88669

8.55
8.41
8.27
8.14
8.01
7.89
7.83
7.77
7.65
7.54
7.43
7.33
7.22
7.12
7.03
6.93
6.89
6.84
6.75
6.66
6.58
6.50
6.46

0.85231
0.85385
0.85544
0.85697
0.85849
0.86001
0.86072
0.86145
0.86291
0.86432
0.86574
0.86710
0.86847
0.86979
0.87113
0.87242
0.87305
0.87368
0.87497
0.87622
0.87745
0.87865
0.87922

9.35
9.17
8.99
8.82
8.65
8.49
8.41
8.34
8.19
8.05
7.91
7.78
7.65
7.53
7.41
7.30
7.24
7.18
7.08
6.97
6.87
6.77
6.72

0.84337
0.84509
0.84672
0.84834
0.84991
0.85150
0.85225
0.85302
0.85453
0.85603
0.85750
0.85894
0.86038
0.86177
0.86316
0.86452
0.86521
0.86587
0.86721
0.86850
0.86977
0.87104
0.87166

9.77
9.59
9.41
9.25
9.08
8.93
8.85
8.78
8.63
8.49
8.36
8.23
8.10
7.98
7.86
7.74
7.69
7.63
7.52
7.42
7.32
7.22
7.17

0.83457
0.83645
0.83821
0.83992
0.84161
0.84327
0.84408
0.84490
0.84651
0.84808
0.84962
0.85115
0.85265
0.85413
0.85559
0.85703
0.85774
0.85845
0.85984
0.86120
0.86253
0.86385
0.86451

10.70
10.40
10.20
10.00
9.80
9.61
9.52
9.43
9.25
9.08
8.92
8.76
8.61
8.46
8.32
8.19
8.12
8.06
7.93
7.81
7.69
7.57
7.52

0.49717

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47

0.86123
0.86269
0.86419
0.86566
0.86713
0.86854
0.86925
0.86994
0.87134
0.87270
0.87404
0.87537
0.87666
0.87796
0.87924
0.88049

8.41
8.28
8.16
8.04
7.93
7.81
7.76
7.71
7.60
7.50
7.40
7.30
7.21
7.12
7.03
6.94

0.85227
0.85387
0.85547
0.85702
0.85854
0.86007
0.86081
0.86155
0.86301
0.86444
0.86584
0.86725
0.86862
0.86998
0.87130
0.87263

9.09
8.94
8.80
8.66
8.53
8.40
8.33
8.27
8.15
8.03
7.92
7.81
7.70
7.60
7.49
7.40

0.84339
0.84510
0.84679
0.84841
0.85005
0.85162
0.85239
0.85318
0.85471
0.85623
0.85771
0.85919
0.86063
0.86206
0.86345
0.86482

9.76
9.59
9.42
9.26
9.11
8.96
8.89
8.82
8.68
8.55
8.42
8.30
8.17
8.06
7.94
7.83

0.83460
0.83651
0.83829
0.84001
0.84173
0.84340
0.84423
0.84505
0.84668
0.84827
0.84982
0.85137
0.85290
0.85439
0.85586
0.85732

10.80
10.60
10.30
10.10
9.92
9.72
9.63
9.54
9.36
9.18
9.02
8.86
8.71
8.56
8.41
8.28

10 T
(MPa1 )
4

(g cm3 )

10 T
(MPa1 )
4

(g cm3 )

104 T
(MPa1 )

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

87

Table 2 (Continued )
x

p (MPa)

T = 298.15 K

T = 308.15 K

T = 318.15 K

T = 328.15 K

(g cm3 )

10 T
(MPa1 )

(g cm3 )

29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.88111
0.88172
0.88294
0.88413
0.88530
0.88648
0.88706

6.90
6.85
6.77
6.69
6.61
6.54
6.50

0.87328
0.87391
0.87519
0.87647
0.87768
0.87891
0.87956

7.35
7.30
7.21
7.12
7.03
6.94
6.90

0.86550
0.86617
0.86753
0.86884
0.87015
0.87143
0.87203

7.78
7.73
7.62
7.52
7.42
7.33
7.28

0.85803
0.85876
0.86016
0.86154
0.86288
0.86421
0.86489

8.21
8.14
8.01
7.89
7.77
7.65
7.59

0.60681

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.86283
0.86429
0.86581
0.86732
0.86879
0.87025
0.87096
0.87169
0.87310
0.87449
0.87584
0.87718
0.87854
0.87984
0.88114
0.88241
0.88304
0.88368
0.88492
0.88611
0.88735
0.88853
0.88911

8.99
8.82
8.65
8.49
8.34
8.19
8.12
8.05
7.91
7.78
7.65
7.53
7.41
7.30
7.19
7.08
7.02
6.97
6.87
6.77
6.68
6.58
6.54

0.85365
0.85528
0.85691
0.85849
0.86004
0.86158
0.86233
0.86310
0.86458
0.86603
0.86748
0.86891
0.87030
0.87168
0.87306
0.87438
0.87504
0.87570
0.87702
0.87828
0.87953
0.88078
0.88141

9.89
9.66
9.45
9.24
9.04
8.85
8.76
8.67
8.49
8.33
8.17
8.01
7.87
7.72
7.59
7.46
7.39
7.33
7.21
7.09
6.97
6.86
6.81

0.84413
0.84590
0.84762
0.84928
0.85093
0.85254
0.85334
0.85414
0.85570
0.85724
0.85876
0.86026
0.86172
0.86319
0.86460
0.86601
0.86671
0.86741
0.86877
0.87010
0.87142
0.87273
0.87337

10.10
9.93
9.75
9.57
9.39
9.23
9.15
9.07
8.91
8.76
8.62
8.48
8.35
8.22
8.09
7.97
7.91
7.85
7.74
7.63
7.52
7.41
7.36

0.83498
0.83693
0.83875
0.84051
0.84226
0.84397
0.84481
0.84566
0.84732
0.84894
0.85054
0.85211
0.85367
0.85520
0.85670
0.85818
0.85892
0.85965
0.86109
0.86249
0.86386
0.86522
0.86590

11.10
10.80
10.60
10.40
10.20
9.95
9.85
9.75
9.56
9.38
9.21
9.04
8.88
8.72
8.58
8.43
8.36
8.29
8.16
8.03
7.90
7.78
7.72

0.70885

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42

0.86437
0.86585
0.86743
0.86895
0.87046
0.87194
0.87268
0.87341
0.87483
0.87626
0.87766
0.87903
0.88037
0.88170

9.08
8.91
8.75
8.59
8.44
8.29
8.22
8.15
8.02
7.89
7.76
7.64
7.52
7.40

0.85492
0.85654
0.85819
0.85983
0.86143
0.86299
0.86375
0.86453
0.86605
0.86755
0.86899
0.87044
0.87187
0.87328

9.95
9.74
9.53
9.33
9.14
8.96
8.87
8.78
8.61
8.45
8.30
8.15
8.00
7.87

0.84536
0.84718
0.84892
0.85062
0.85230
0.85394
0.85476
0.85556
0.85716
0.85874
0.86028
0.86180
0.86331
0.86479

10.60
10.40
10.10
9.93
9.72
9.52
9.43
9.33
9.15
8.97
8.80
8.64
8.49
8.34

0.83600
0.83798
0.83983
0.84164
0.84344
0.84517
0.84605
0.84690
0.84859
0.85027
0.85191
0.85348
0.85508
0.85666

11.70
11.40
11.10
10.80
10.60
10.30
10.20
10.10
9.86
9.64
9.44
9.24
9.05
8.87

10 T
(MPa1 )
4

(g cm3 )

10 T
(MPa1 )
4

(g cm3 )

104 T
(MPa1 )

88

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

Table 2 (Continued )
x

p (MPa)

T = 298.15 K

T = 308.15 K

T = 318.15 K

T = 328.15 K

(g cm3 )

10 T
(MPa1 )

(g cm3 )

26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.88302
0.88435
0.88495
0.88559
0.88687
0.88809
0.88932
0.89052
0.89113

7.29
7.19
7.13
7.08
6.98
6.88
6.79
6.69
6.65

0.87467
0.87601
0.87670
0.87736
0.87871
0.87999
0.88128
0.88257
0.88323

7.73
7.60
7.54
7.48
7.36
7.24
7.13
7.02
6.97

0.86622
0.86766
0.86838
0.86909
0.87046
0.87183
0.87316
0.87450
0.87515

8.19
8.05
7.98
7.92
7.79
7.66
7.54
7.42
7.37

0.85815
0.85969
0.86044
0.86118
0.86267
0.86408
0.86550
0.86687
0.86757

8.70
8.53
8.45
8.37
8.22
8.07
7.92
7.79
7.72

0.79512

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.86629
0.86783
0.86942
0.87101
0.87256
0.87410
0.87484
0.87559
0.87707
0.87851
0.87994
0.88137
0.88274
0.88414
0.88547
0.88682
0.88748
0.88814
0.88940
0.89067
0.89195
0.89319
0.89382

9.35
9.17
9.00
8.83
8.67
8.52
8.45
8.37
8.23
8.09
7.96
7.83
7.71
7.59
7.48
7.36
7.31
7.26
7.15
7.05
6.95
6.85
6.81

0.85647
0.85814
0.85982
0.86148
0.86310
0.86470
0.86548
0.86627
0.86781
0.86934
0.87082
0.87230
0.87376
0.87518
0.87659
0.87797
0.87866
0.87934
0.88071
0.88202
0.88333
0.88462
0.88527

10.10
9.84
9.64
9.44
9.25
9.07
8.98
8.90
8.73
8.57
8.42
8.27
8.13
7.99
7.86
7.73
7.67
7.61
7.49
7.37
7.26
7.15
7.10

0.84664
0.84848
0.85026
0.85198
0.85371
0.85538
0.85622
0.85704
0.85867
0.86027
0.86185
0.86340
0.86493
0.86645
0.86792
0.86938
0.87011
0.87084
0.87225
0.87363
0.87500
0.87636
0.87702

10.70
10.50
10.30
10.10
9.86
9.66
9.57
9.47
9.29
9.12
8.96
8.80
8.64
8.49
8.35
8.21
8.14
8.08
7.95
7.82
7.70
7.59
7.53

0.83688
0.83890
0.84079
0.84263
0.84446
0.84623
0.84711
0.84800
0.84972
0.85142
0.85308
0.85471
0.85634
0.85792
0.85948
0.86102
0.86178
0.86255
0.86405
0.86550
0.86693
0.86834
0.86904

11.70
11.40
11.10
10.90
10.60
10.40
10.30
10.20
9.97
9.77
9.57
9.39
9.21
9.04
8.87
8.71
8.63
8.56
8.41
8.27
8.13
8.00
7.93

0.89947

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37

0.86961
0.87118
0.87283
0.87445
0.87603
0.87761
0.87836
0.87912
0.88064
0.88215
0.88361
0.88505

9.73
9.53
9.33
9.15
8.97
8.79
8.71
8.63
8.47
8.31
8.17
8.02

0.85913
0.86086
0.86258
0.86427
0.86591
0.86755
0.86837
0.86916
0.87074
0.87229
0.87383
0.87533

10.10
9.93
9.74
9.55
9.37
9.20
9.12
9.03
8.87
8.72
8.57
8.43

0.84893
0.85082
0.85265
0.85443
0.85618
0.85793
0.85878
0.85963
0.86130
0.86296
0.86457
0.86615

11.00
10.70
10.50
10.30
10.10
9.88
9.78
9.69
9.51
9.33
9.16
9.00

0.83856
0.84062
0.84256
0.84445
0.84633
0.84817
0.84908
0.84998
0.85176
0.85349
0.85520
0.85686

11.70
11.40
11.20
10.90
10.70
10.50
10.40
10.30
10.10
9.93
9.75
9.58

10 T
(MPa1 )
4

(g cm3 )

10 T
(MPa1 )
4

(g cm3 )

104 T
(MPa1 )

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

89

Table 2 (Continued )
x

1.00000

p (MPa)

T = 298.15 K

T = 308.15 K

T = 318.15 K

T = 328.15 K

(g cm3 )

10 T
(MPa1 )

(g cm3 )

22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.88646
0.88790
0.88927
0.89065
0.89134
0.89201
0.89334
0.89465
0.89594
0.89720
0.89785

7.89
7.75
7.63
7.50
7.44
7.38
7.27
7.16
7.05
6.94
6.89

0.87682
0.87829
0.87973
0.88116
0.88187
0.88255
0.88395
0.88528
0.88663
0.88794
0.88861

8.29
8.16
8.03
7.90
7.84
7.78
7.66
7.55
7.44
7.33
7.28

0.86773
0.86927
0.87079
0.87230
0.87306
0.87382
0.87523
0.87667
0.87806
0.87943
0.88011

8.84
8.69
8.54
8.40
8.33
8.27
8.13
8.01
7.88
7.77
7.71

0.85854
0.86015
0.86177
0.86335
0.86413
0.86492
0.86644
0.86793
0.86939
0.87083
0.87154

9.41
9.25
9.10
8.95
8.88
8.81
8.67
8.53
8.41
8.28
8.22

0.10
2.13
4.15
6.18
8.21
10.23
11.25
12.26
14.29
16.31
18.34
20.37
22.39
24.42
26.45
28.47
29.49
30.50
32.53
34.55
36.58
38.60
39.62

0.87356
0.87516
0.87681
0.87844
0.88004
0.88161
0.88240
0.88319
0.88472
0.88619
0.88767
0.88913
0.89055
0.89197
0.89337
0.89476
0.89543
0.89611
0.89744
0.89876
0.90007
0.90135
0.90200

9.41
9.25
9.09
8.94
8.79
8.65
8.58
8.51
8.38
8.25
8.13
8.01
7.89
7.78
7.67
7.56
7.51
7.46
7.36
7.26
7.16
7.07
7.03

0.86290
0.86466
0.86642
0.86815
0.86984
0.87152
0.87235
0.87317
0.87477
0.87635
0.87794
0.87946
0.88099
0.88246
0.88394
0.88539
0.88611
0.88683
0.88822
0.88962
0.89099
0.89232
0.89297

10.40
10.20
9.97
9.77
9.58
9.39
9.30
9.21
9.04
8.87
8.72
8.56
8.42
8.27
8.14
8.00
7.94
7.88
7.75
7.63
7.52
7.41
7.35

0.85209
0.85399
0.85583
0.85765
0.85946
0.86122
0.86208
0.86296
0.86465
0.86633
0.86800
0.86960
0.87119
0.87276
0.87432
0.87584
0.87659
0.87735
0.87884
0.88029
0.88171
0.88313
0.88384

11.00
10.80
10.60
10.30
10.10
9.96
9.87
9.78
9.60
9.43
9.27
9.12
8.97
8.82
8.68
8.54
8.48
8.41
8.28
8.16
8.04
7.92
7.87

0.84128
0.84333
0.84532
0.84729
0.84921
0.85110
0.85203
0.85295
0.85477
0.85654
0.85830
0.86001
0.86173
0.86337
0.86503
0.86664
0.86742
0.86823
0.86979
0.87130
0.87283
0.87432
0.87502

11.80
11.60
11.40
11.10
10.90
10.70
10.60
10.50
10.30
10.10
9.94
9.76
9.60
9.44
9.28
9.13
9.06
8.99
8.85
8.71
8.58
8.45
8.39

10 T
(MPa1 )
4

(g cm3 )

10 T
(MPa1 )
4

(g cm3 )

104 T
(MPa1 )

It was found that parameters C and D are correlated and the objective function has a great many local
minima. The global minimum was therefore determined by non-deterministic minimisation algorithm
ES2 developed by Tvrdk and Kriv [14]. The algorithm requires a few parameters, which must be
properly set. In this work, the size of the pool is 10 nodes. The new pool in each iteration step inherits
five nodes with the lowest value of the objective function. The probability at which the node with an
increase of the objective function is accepted was set to 0.05. The initial pool contained 10 randomly
generated nodes uniformly distributed in the square satisfying 0.01 < C < 20 and 0.1 < D < 250.

90

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

Fig. 1. Isothermal compressibility T for x benzene + (1 x) 1,3,5-trimethylbenzene at T = 328.15 K: () x = 0.00000;

() x = 0.19391; () x = 0.43460; () x = 0.60681; (+) x = 0.79512; () x = 1.00000.

It was verified by repeated calculations that these settings guarantee that the global minimum is always
reached.
The optimised parameters C and D of the Tait equation along with the standard deviations in density
are given in Table 3. It is evident that the equation fits accurately the densities over the entire pressure
range.
3.2. Isothermal compressibilities
The isothermal compressibility T was calculated from the equation


 

C
1 V

T =
=
,
V p T,x 0 D + p

(4)

where V is the molar volume. The values of T are given in Table 2 and illustrated in Fig. 1 for the temperature of 328.15 K. They increase monotonously with increasing temperature in the given temperature
range.
3.3. Excess molar volumes
The values of VmE were calculated from the mixtures densities, , and the densities, i , and molar
masses, Mi , of pure components i (i = 1 and 2) using the relation
VmE =

xM1 + (1 x)M2 xM1 (1 x)M2

1
2

(5)

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

91

Table 3
Coefficients C and D of the Tait equation (Eq. (2)) for x benzene + (1 x) 1,3,5-trimethylbenzene at temperature T and
standard deviations of the fit
T (K)

102 C

D (MPa)

105 (g cm3 )

298.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

9.5221
8.2920
8.8510
8.8956
9.2837
10.0000
8.5149
8.7916
8.8552
8.3949
9.7066

120.0914
98.6747
105.4166
105.2774
108.4189
118.7828
94.5882
96.7004
94.6388
86.1419
103.0082

6
3
2
3
4
16
3
2
2
6
4

308.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

8.3866
10.0000
10.0000
8.9436
8.4952
10.0000
7.8103
8.2662
8.5491
9.1055
8.8456

96.5685
117.7840
116.3515
99.2341
90.7228
109.9046
78.8602
82.9404
84.9284
89.7098
84.9233

1
9
9
3
2
11
7
5
3
1
2

318.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

8.9658
9.9213
10.0000
9.1390
9.4516
10.0000
9.4595
8.5289
8.9025
9.1216
9.6791

98.0183
108.7366
108.2913
95.2044
96.6350
102.3909
93.2957
80.2462
82.8579
83.0771
87.9827

3
7
9
3
4
9
4
3
2
2
3

328.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

9.5747
10.0000
10.0000
8.7059
8.9848
9.0401
8.9727
8.0470
8.7001
9.7211
10.0000

99.5464
102.8135
101.5355
83.2743
84.2059
83.7152
80.9032
68.5701
74.3007
83.3075
84.3040

7
10
13
2
3
3
2
9
3
6
7

92

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

Fig. 2. Excess molar volumes VmE for x benzene + (1x) 1,3,5-trimethylbenzene at T = 328.15 K. Pressures: () 2.13 MPa,
experimental points, ( - - ) calculated from Eq. (6); () 11.25 MPa, experimental points, () calculated from Eq. (6); ()
20.37 MPa, experimental points, (- - -) calculated from Eq. (6); () 29.50 MPa, experimental points, ( ) calculated from
Eq. (6); () 38.60 MPa, experimental points, ( - ) calculated from Eq. (6).

where subscript 1 refers to benzene and subscript 2 to 1,3,5-trimethylbenzene and x stands for the mole
fraction of benzene.
The experimental uncertainty in the VmE is estimated to be about 1 102 cm3 mol1 , which is
about five times worse compared to measurements at T = 298.15 K and atmospheric pressure. The
measurements at high pressures naturally worsen the uncertainty owing to hysteresis of the densimeter
vibrating-tube and error in the pressure measurement. The values of excess volumes VmE at five chosen
pressures equal approximately to 2, 11, 20, 29, and 38 MPa are given in Table 4.
The VmE data were fitted to the RedlichKister equation

 2

VmE = x(1 x)
An (1 2x)n .

(6)

n=0

The coefficients An and standard deviations (VmE ) of the fit are summarised in Table 5. The number of
parameters An was predetermined by the statistical F-test.
The illustration of the pressure dependence of VmE is given in Fig. 2 for the temperature of 328.15 K.
From the analogous figures for all the temperatures follows that the VmE curves are shifted in a regular way
with increasing temperature and pressure. The decrease in VmE values with increasing temperature follows
the temperature dependence of VmE at atmospheric pressure [8]. The pressure dependence at constant
temperature is also regular. The VmE values are apparently decreasing with increasing pressure for the
same composition. The positions of maxima on the curves are only slightly shifted with pressure.

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

93

Table 4
Excess molar volume VmE in (cm3 mol1 ) for x benzene + (1 x) 1,3,5-trimethylbenzene at temperature T and pressure p
T (K)

p (MPa)
2.13

11.25

20.37

29.50

38.60

298.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

0.000
0.165
0.305
0.439
0.553
0.615
0.559
0.517
0.420
0.225
0.000

0.000
0.153
0.292
0.430
0.541
0.601
0.548
0.503
0.401
0.209
0.000

0.000
0.143
0.282
0.415
0.529
0.590
0.540
0.493
0.385
0.194
0.000

0.000
0.128
0.264
0.405
0.517
0.577
0.526
0.485
0.369
0.178
0.000

0.000
0.123
0.254
0.402
0.508
0.571
0.518
0.480
0.359
0.167
0.000

308.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

0.000
0.238
0.362
0.454
0.547
0.610
0.543
0.504
0.419
0.253
0.000

0.000
0.237
0.363
0.445
0.531
0.594
0.533
0.492
0.409
0.247
0.000

0.000
0.229
0.357
0.435
0.517
0.580
0.517
0.480
0.398
0.240
0.000

0.000
0.220
0.343
0.421
0.505
0.566
0.507
0.469
0.389
0.231
0.000

0.000
0.227
0.344
0.418
0.497
0.558
0.500
0.460
0.382
0.227
0.000

318.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

0.000
0.212
0.342
0.433
0.534
0.579
0.557
0.479
0.398
0.231
0.000

0.000
0.206
0.330
0.421
0.522
0.561
0.540
0.465
0.384
0.217
0.000

0.000
0.200
0.322
0.411
0.512
0.545
0.527
0.455
0.374
0.210
0.000

0.000
0.195
0.312
0.404
0.500
0.535
0.514
0.444
0.363
0.197
0.000

0.000
0.192
0.311
0.397
0.492
0.524
0.506
0.438
0.357
0.195
0.000

328.15

0.00000
0.10849
0.19391
0.29799
0.43460
0.49717
0.60681
0.70885
0.79512
0.89947
1.00000

0.000
0.199
0.333
0.394
0.497
0.519
0.513
0.429
0.364
0.228
0.000

0.000
0.190
0.320
0.379
0.481
0.504
0.501
0.418
0.357
0.221
0.000

0.000
0.189
0.312
0.371
0.471
0.493
0.490
0.411
0.349
0.217
0.000

0.000
0.180
0.299
0.359
0.457
0.479
0.476
0.397
0.339
0.207
0.000

0.000
0.179
0.302
0.354
0.451
0.472
0.469
0.393
0.334
0.206
0.000

94

L. Moravkova et al. / Fluid Phase Equilibria 209 (2003) 8194

Table 5
Coefficient Ai of the RedlichKister equation (Eq. (6)) and standard deviations (VmE ) determined by the maximum likelihood
principle for x benzene + (1 x) 1,3,5-trimethylbenzene at temperature T and pressure p
T/K

p/MPa

A0 /(cm3 mol1 )

A1 /(cm3 mol1 )

A2 /(cm3 mol1 )

102 VmE /(cm3 mol1 )

298.15

2.13
11.25
20.37
29.50
38.60

2.3579
2.3141
2.2759
2.2345
2.2117

0.4837
0.4576
0.4534
0.4567
0.4451

0.3549
0.5047
0.6354
0.7946
0.8826

1.58
1.46
1.44
1.57
1.71

308.15

2.13
11.25
20.37
29.50
38.60

2.2868
2.2276
2.1728
2.1232
2.0898

0.2337
0.2013
0.1935
0.2051
0.1636

0.4187
0.4824
0.4660
0.4024
0.4513

2.03
1.94
1.95
1.86
1.91

318.15

2.13
11.25
20.37
29.50
38.60

2.2426
2.1822
2.1344
2.0917
2.0551

0.2573
0.2357
0.2309
0.2066
0.2015

0.1324
0.0720
0.0560
0.0103
0.0181

1.35
1.21
1.05
1.07
1.00

328.15

2.13
11.25
20.37
29.50
38.60

2.0347
1.9775
1.9349
1.8821
1.8533

0.1997
0.2273
0.2196
0.2233
0.2062

0.2978
0.2727
0.2799
0.2210
0.2610

1.70
1.69
1.60
1.51
1.61

Acknowledgements
The authors would like to acknowledge the partial support of the Grant Agency of the Czech Republic.
The work has been carried out under grant no. 203/02/1098.
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