J. Chem.

Thermodynamics 44 (2012) 133–147

Contents lists available at SciVerse ScienceDirect

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

Compressed liquid densities for the (n-heptane + n-decane) and

(n-octane + n-decane) systems from T = (313 to 363) K
Rodolfo Quevedo-Nolasco a, Luis A. Galicia-Luna a,⇑, Octavio Elizalde-Solis b
a
Laboratorio de Termodinámica, SEPI-ESIQIE, Instituto Politécnico Nacional, UPALM, Ed. Z, Secc. 6, 1ER piso, Lindavista, C.P. 07738 México D.F., Mexico
b
Departamento de Ingeniería Química Petrolera, ESIQIE, Instituto Politécnico Nacional, UPALM, Edif. 8, 2° piso, Lindavista, C.P. 07738 México D.F., Mexico

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

Article history: Densities (p, q, T, x1) of two binary n-alkane systems are reported from T = (313 to 363) K in the
Received 16 June 2011 compressed liquid phase up to 25 MPa over the whole range of composition. The binary mixtures {x1n-
Received in revised form 12 August 2011 heptane + (1  x1)n-decane} and {x1n-octane + (1  x1)n-decane} were prepared at compositions of
Accepted 13 August 2011
(x1 = 0.0531, 0.2594, 0.5219, 0.777, 0.952), and (x1 = 0.0616, 0.2801, 0.5314, 0.7736, 0.9623), respectively.
Available online 22 August 2011
A measuring system based on a vibrating tube densimeter, DMA HPM from Anton Paar with data
acquisition system was developed in order to obtain experimental densities. Water and nitrogen were
Keywords:
used as reference fluids to calibrate the densimeter. Experimental methodology was checked by compar-
n-Heptane
n-Octane
ing the n-heptane and n-decane densities against multi-parameter equations proposed in the literature.
n-Decane Differences between both sets of data show a maximum deviation of 0.07%. Excess molar volumes,
Density isothermal compressibility and isobaric thermal expansivity were computed from experimental
Vibrating tube densimeter densities.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction over a wide temperature range of (293 to 557) K. The volumetric

behaviour of (n-hexane + n-decane, n-octane + n-dodecane,
Thermodynamic properties obtained through experimentation n-decane + n-tetradecane) systems is reported by Takagi and
are the fundamental basis for the development of empirical, Teranishi [15] for no more than three pressures (0.1, 50, and
semi-empirical or theoretical models used to represent and predict 100) MPa at T = 298 K. Experimental densities for the binary
the behaviour of fluids. Volumetric properties are important in (n-decane + n-tetradecane, n-dodecane + n-hexadecane) and
chemical engineering for the design, simulation and optimisation ternary (n-decane + n-tetradecane + n-hexadecane) mixtures were
of various separation processes, such as distillation, absorption, studied at a maximum pressure of 430 MPa in reference [16].
desorption, drying, liquid–liquid extraction, extraction with super- Densities for n-pentane, n-hexane and n-heptane and their binary
critical fluids. Knowledge of the density at different temperatures and ternary mixtures were measured elsewhere [17] from (0.1 to
and pressures is also essential for the calculation of properties such 40) MPa at T = (298, 323, and 348) K. A bellows volumometer
as solubility or viscosity, both crucial in different fields of was used to obtain density data for the (n-hexane + n-dodecane,
technology. n-octane + n-dodecane and n-hexane + n-hexadecane) systems at
A survey of studies during the last century of liquid densities for temperatures T = (298, 323, 348, and 373) K over the pressure
n-alkane mixtures has been collected by Aalto et al. [1]. Most of the range of (0.1 to 500) MPa [18,19].
density data for binary n-alkane mixtures reported in the literature Densities for n-alkane mixtures from the above mentioned
were studied at atmospheric pressure and low temperatures references were measured in piezometer devices [14–16] and a
between (283 and 298) K [2–11]; therefore the corresponding commercial vibrating tube densimeter [17]. The excess molar vol-
ternary systems are scarce even for temperatures higher than umes exhibit the highest negative values approximately in the
373 K [11–13]. equimolar composition. However, some systems present both neg-
Volumetric properties at high pressure were published else- ative and positive values [16]. For binary mixtures at atmospheric
where for a homogeneous liquid phase [14–19]. Abdulagatov and pressure, the values of excess molar volume are closer to zero
Azizov [14] investigated the (p, q, T, x1) behaviour for the when the carbon number of both compounds is nearly identical.
(n-heptane + n-octane) system at a maximum pressure of 10 MPa The only density data for the (n-heptane + n-decane and
n-octane + n-decane) system are reported at atmospheric pressure
and T = 293 K by Cooper and Asfour [3] using a vibrating tube
⇑ Corresponding author. Tel.: +52 55 5729 6000x55133; fax: +52 55 5586 2728. densimeter. Compressed liquid density data for the (n-hep-
E-mail address: lgalicial@ipn.mx (L.A. Galicia-Luna). tane + n-decane) system are reported by Assael et al. [20] at

0021-9614/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2011.08.016
134 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147

FIGURE 1. Experimental apparatus with data acquisition configuration: 1, vibrating tube densimeter; 2, loading cell; 3, oven; 4, syringe pump; 5, circulating liquid bath; 6,
evaluation unit. 7; temperature indicator; 8, multimeter; 9, serial interface adapter; 10, nitrogen cylinder; 11, stirring system; and 12, power supply.

pressures from (0.1 to 71) MPa and temperatures of (313 and 2.2. Apparatus
323) K; nevertheless those values are calculated from densities of
pure compounds assuming ideal behaviour. A schematic diagram of the experimental apparatus developed
The purpose of this work is to present the experimental density in this work is shown in figure 1. The measuring principle is based
behaviour, computed excess molar volume and derivative proper-
ties of n-alkane binary mixtures in the compressed liquid region.
Densities of the binary (n-heptane + n-decane) and (n-octane + n- TABLE 2
decane) systems were obtained over the whole range of composi- Experimental densities for n-heptane.a

tion from T = (313.15 to 363.15) K and up to 25 MPa. p/MPa q/(kg  m3) p/MPa q/(kg  m3) p/MPa q/(kg  m3)
T = 313.18 K T = 333.04 K T = 353.06 K
1.00 668.09 1.00 650.66 1.01 632.60
2.00 669.03 2.00 651.80 2.00 634.02
2. Experimental
3.00 669.97 3.00 652.94 3.00 635.41
4.00 670.93 4.00 654.08 4.00 636.78
2.1. Materials 5.01 671.90 5.00 655.23 5.00 638.15
6.00 672.87 6.00 656.38 6.00 639.47
7.00 673.86 7.00 657.54 7.00 640.80
The n-alkanes and water were supplied by Sigma–Aldrich. Infra
8.00 674.87 8.00 658.65 8.00 642.10
Air Products supplied nitrogen. A Karl-Fischer coulometer (831, 9.00 675.87 9.00 659.81 9.01 643.40
Metrohm) was used to determine the water content of n-alkanes. 10.00 676.86 10.00 660.92 10.00 644.66
Chemicals were not purified further and were used as received. 11.00 677.85 11.00 662.03 11.00 645.92
Certified purities and water content of the compounds are given 12.00 678.83 12.00 663.10 12.00 647.13
13.00 679.81 13.00 664.20 13.00 648.37
in table 1.
14.00 680.76 14.00 665.25 14.00 649.56
15.00 681.70 15.00 666.31 15.00 650.72
16.00 682.62 16.00 667.33 16.00 651.88
TABLE 1 17.00 683.53 17.00 668.33 17.00 653.00
Chemicals used in this work. 18.00 684.41 18.03 669.34 18.03 654.12
19.00 685.26 19.00 670.26 19.00 655.16
CAS Supplier Mol fraction Mol fraction 20.00 686.11 20.00 671.20 20.00 656.22
purity water 21.00 686.92 21.00 672.10 21.00 657.27
22.00 687.67 22.00 673.01 22.00 658.25
n-Heptane 142-82-5 Sigma–Aldrich 0.993 17  105
23.00 688.42 23.00 673.86 23.00 659.24
n-Octane 111-65-9 Sigma–Aldrich 0.99 18  105
23.91 689.07 24.00 674.70 24.00 660.20
n-Decane 124-18-5 Sigma–Aldrich 0.997 28  105
25.00 689.85 25.00 675.52 25.00 661.14
Water 7732-18-5 Sigma–Aldrich 0.9995 N.D.
Nitrogen 7727-37-9 Air Products-Infra 0.99998 N.D. a
Standard uncertainties u are u(T) = 0.03 K, u(p) = 0.02 MPa, u(q) = 0.095 kg  m3.
Expanded uncertainty U is U(q) = 0.19 kg  m3 (0.95 level of confidence).
N.D.: not determined.
 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147 135

TABLE 3
Experimental densities for n-decane.a

p/MPa q/(kg  m3) p/MPa q/(kg  m3) p/MPa q/(kg  m3) p/MPa q/(kg  m3) p/MPa q/(kg  m3) p/MPa q/(kg  m3)
T = 313.07 K T = 323.00 K T = 332.87 K T = 342.78 K T = 352.80 K T = 362.73 K
1.00 715.64 1.00 707.96 1.00 700.33 1.00 692.65
2.00 716.68 2.00 708.93 2.00 701.26 2.00 693.68 2.00 686.08 2.00 678.44
3.00 717.38 3.00 709.81 3.00 702.21 3.00 694.72 3.00 687.17 3.00 679.58
4.00 718.16 4.00 710.88 4.00 703.17 4.00 695.70 4.00 688.23 4.00 680.71
5.00 719.02 5.00 711.52 5.00 704.12 5.00 696.68 5.00 689.30 5.00 681.85
6.00 719.65 6.00 712.48 6.00 705.07 6.00 697.68 6.00 690.33 6.00 682.98
7.00 720.52 7.00 713.30 7.00 705.98 7.00 698.61 7.00 691.38 7.00 684.09
8.00 721.28 8.00 714.23 8.00 706.88 8.00 699.57 8.00 692.38 8.00 685.16
9.00 722.11 9.00 715.05 9.00 707.79 9.00 700.54 9.00 693.41 9.00 686.25
10.00 723.13 10.00 715.91 10.00 708.65 10.00 701.49 10.00 694.37 10.00 687.29
11.00 723.65 11.00 716.74 11.00 709.52 11.00 702.40 11.00 695.36 11.00 688.32
12.00 724.48 12.00 717.54 12.00 710.39 12.00 703.29 12.00 696.32 12.00 689.33
13.00 725.48 13.00 718.35 13.00 711.26 13.00 704.14 13.00 697.29 13.00 690.34
14.00 726.15 14.00 719.15 14.00 712.07 14.00 705.05 14.00 698.22 14.00 691.28
15.00 726.86 15.00 719.92 15.00 712.90 15.00 705.93 15.00 699.15 15.00 692.36
16.00 727.49 16.00 720.70 16.00 713.71 16.00 706.79 16.00 700.03
17.00 728.18 17.00 721.46 17.00 714.52 17.00 707.60 17.00 700.94
18.00 729.07 18.00 722.22 18.00 715.32 18.01 708.57 18.00 701.82
19.00 729.72 19.00 722.97 19.00 716.10 19.00 709.45 19.00 702.71
20.00 730.26 20.00 723.71 20.00 716.88 20.00 710.30 20.00 703.59
21.00 731.22 21.00 724.45 21.00 717.65 21.00 710.91 21.00 704.44
22.00 731.80 22.00 725.18 22.00 718.43 22.00 711.92 22.00 705.25
23.00 732.70 23.00 725.92 23.00 719.19 23.00 712.48 23.00 706.14
24.00 733.26 24.00 726.62 24.00 719.99 24.00 713.42 24.00 706.95
25.00 733.93 25.00 727.42 25.00 720.76 25.00 714.10 25.00 707.83
a
Standard uncertainties u are u(T) = 0.03 K, u(p) = 0.02 MPa, u(q) = 0.095 kg  m3. Expanded uncertainty U is U(q) = 0.19 kg  m3 (0.95 level of confidence).

FIGURE 2. Plot of deviations between experimental densities qexp for n-heptane measured in this work and the proposed equation by Schilling et al. [27] qcal against pressure.
T = (d) 313.18 K, (5) 333.04 K, (j) 353.06 K. Horizontal dashed lines represent equation uncertainty.

on the static – synthetic method. A vibrating tube densimeter The Anton Paar DMA – HPM densimeter contains a U-shaped
(VTD); 1, connected through tubing to a loading cell 2, are the main Hastelloy C-276 tube with a sample capacity of 2 cm3. The range
components to perform density measurements for the systems of measurement for temperature is from (263.15 to 473.15) K
studied. A needle valve allows the homogeneous fluid contained and can be operated at a maximum pressure of 140 MPa. A piston
in the loading cell to flow and fill the VTD. inside the cell separates the studied fluid from the pressurising
136 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147

fluid. Pressure is increased by high purity nitrogen from a supply

cylinder 10. When the cylinder pressure is insufficient, an Isco syr-
inge-type pump (Model: 100 DM) 4, is used to generate higher
pressure.
An oven 3. (France Etuves: XL074SP) is used to control the load-
ing cell temperature while the VTD temperature, also located in-
side the oven, is kept constant by a circulating liquid bath
(Polyscience: 9510) 5. The stirring system consists of a variable
speed motor (Model: RZR 2020, Heidolph) 11. It has two magnetic
bars embedded and makes to spin a magnetic bar placed inside the
cell.
A Bourdon-Sedeme transducer (Model: S242) located on the cell
cap is connected to a power supply (Model: E3610A, HP); 12, and
in turn to a digital multimeter (Model: 34401A, HP) 8, for pressure
reading. Although the VTD has an internal temperature sensor
connected to the Anton Paar evaluation unit 6, this variable was
measured by means of two calibrated platinum resistance ther-
mometers PT-100-X inserted in the middle of the VTD and at the
FIGURE 3. Density deviations for n-decane. Plot of experimental densities qexp from top of the loading cell. Thermometers send the signals to a digital
this work against those calculated qcal with the equation proposed by Lemmon and temperature indicator (ARK: F-250) 7, to read these values. The
Span [32] against pressure. T = (d) 313.07 K, (5) 323.00 K, (j) 332.87 K, (})
342.78 K, (N) 352.80 K, ( ) 362.73 K.
vibrating period of VTD is displayed on the evaluation unit (Model:
mPDS 2000V3) with a resolution of 1  103 ls.

TABLE 4
Experimental densities for the binary mixture {n-heptane (1) + n-decane (2)} at x1 = 0.0531.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.16 K T = 323.15 K T = 333.12 K
1.00 713.67 1.062 1.272 705.96 1.088 1.366 698.20 1.109 1.463
2.00 714.44 1.053 1.252 706.92 1.078 1.344 699.22 1.099 1.439
3.00 715.27 1.044 1.232 707.86 1.069 1.323 700.22 1.090 1.416
4.00 716.08 1.035 1.213 708.79 1.060 1.302 701.18 1.080 1.394
5.00 716.94 1.027 1.194 709.69 1.051 1.281 702.16 1.071 1.372
6.00 717.67 1.018 1.175 710.58 1.042 1.261 703.10 1.062 1.350
7.00 718.51 1.010 1.157 711.49 1.033 1.242 704.05 1.053 1.329
8.00 719.34 1.001 1.140 712.35 1.025 1.223 704.99 1.044 1.309
9.00 720.13 0.993 1.122 713.20 1.016 1.205 705.90 1.036 1.289
10.00 721.00 0.985 1.106 714.07 1.008 1.186 706.80 1.027 1.269
10.99 721.80 0.977 1.089 714.90 1.000 1.169 707.69 1.019 1.251
12.00 722.62 0.970 1.073 715.73 0.992 1.151 708.56 1.010 1.232
13.00 723.44 0.962 1.057 716.54 0.984 1.134 709.43 1.002 1.214
14.00 724.26 0.954 1.042 717.35 0.976 1.118 710.28 0.994 1.196
15.00 725.05 0.947 1.027 718.14 0.968 1.102 711.14 0.987 1.178
16.00 725.84 0.940 1.012 718.92 0.961 1.086 711.96 0.979 1.161
17.00 726.57 0.933 0.998 719.70 0.954 1.070 712.79 0.971 1.145
18.00 727.29 0.926 0.984 720.46 0.946 1.055 713.60 0.964 1.128
19.00 728.02 0.919 0.970 721.21 0.939 1.040 714.39 0.956 1.112
20.00 728.71 0.912 0.957 721.96 0.932 1.026 715.18 0.949 1.097
21.00 729.39 0.905 0.943 722.70 0.925 1.011 715.96 0.942 1.081
22.00 730.07 0.898 0.930 723.41 0.918 0.997 716.72 0.935 1.066
23.00 730.67 0.892 0.918 724.12 0.911 0.984 717.46 0.928 1.052
24.00 731.27 0.885 0.905 724.82 0.905 0.970 718.21 0.921 1.037
25.00 731.84 0.879 0.893 725.51 0.898 0.957 718.95 0.914 1.023
T = 343.09 K T = 353.06 K T = 363.03 K
1.00 690.42 1.128 1.562 682.62 1.143 1.665 674.85 1.157 1.769
2.00 691.49 1.118 1.537 683.77 1.133 1.637 676.04 1.146 1.740
3.00 692.55 1.108 1.512 684.88 1.123 1.611 677.23 1.136 1.712
4.00 693.59 1.098 1.488 685.98 1.113 1.585 678.38 1.126 1.684
5.00 694.62 1.089 1.465 687.07 1.103 1.560 679.52 1.116 1.657
6.00 695.63 1.079 1.442 688.13 1.094 1.535 680.65 1.106 1.631
7.00 696.62 1.070 1.419 689.17 1.084 1.511 681.75 1.097 1.605
8.00 697.60 1.061 1.397 690.21 1.075 1.488 682.84 1.087 1.580
9.00 698.57 1.052 1.376 691.24 1.066 1.465 683.92 1.078 1.556
10.00 699.52 1.043 1.355 692.24 1.057 1.442 684.98 1.069 1.532
11.00 700.46 1.035 1.334 693.24 1.048 1.420 686.02 1.060 1.508
12.00 701.38 1.026 1.314 694.22 1.040 1.399 687.05 1.051 1.486
13.00 702.30 1.018 1.295 695.18 1.031 1.378 688.07 1.042 1.463
14.00 703.21 1.010 1.276 696.13 1.023 1.358 689.07 1.033 1.441
15.00 704.09 1.002 1.257 697.07 1.014 1.338 690.05 1.025 1.420
16.00 704.98 0.994 1.239 698.00 1.006 1.318 691.03 1.017 1.399
17.00 705.84 0.986 1.221 698.90 0.998 1.299 691.98 1.009 1.379
18.00 706.70 0.978 1.203 699.80 0.990 1.280 692.93 1.001 1.359
 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147 137

TABLE 4 (continued)

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
19.00 707.54 0.971 1.186 700.69 0.983 1.262 693.87 0.993 1.339
20.00 708.37 0.963 1.169 701.57 0.975 1.244 694.79 0.985 1.320
21.00 709.20 0.956 1.153 702.43 0.968 1.226 695.70 0.977 1.301
22.00 710.00 0.949 1.137 703.30 0.960 1.209 696.60 0.970 1.283
23.00 710.80 0.942 1.121 704.13 0.953 1.192 697.47 0.962 1.265
24.00 711.58 0.935 1.106 704.96 0.946 1.176 698.37 0.955 1.248
25.00 712.36 0.928 1.091 705.78 0.939 1.160 699.21 0.948 1.230
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.

In order to observe directly the system behaviour, the experi- a multi-parallel RS-232/USB serial interface adapter (Model: 2403,
mental vibrating period, temperature and pressure are registered Sealevel) 9.
and plotted quasi-simultaneously every 5 s using a data acquisition For a successful experimentation, the measuring instruments
program (Agilent, VEE 7.0). The multimeter, temperature indicator are necessary to calibrate with suitable reference standards. The
and evaluation unit are communicated with the computer through calibration of thermometers was performed using a resistance

TABLE 5
Experimental densities for the binary mixture {n-heptane (1) + n-decane (2)} at x1 = 0.2594.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.16 K T = 323.15 K T = 333.14 K
1.00 706.37 1.103 1.323 698.56 1.124 1.423 690.74 1.141 1.527
2.00 707.17 1.093 1.301 699.45 1.114 1.400 691.66 1.131 1.502
3.00 707.97 1.083 1.280 700.30 1.104 1.377 692.62 1.121 1.477
4.00 708.78 1.074 1.259 701.18 1.094 1.354 693.57 1.111 1.452
5.00 709.65 1.065 1.239 702.06 1.084 1.332 694.49 1.101 1.429
6.00 710.50 1.055 1.219 702.96 1.075 1.311 695.43 1.091 1.406
7.00 711.35 1.046 1.200 703.89 1.066 1.290 696.40 1.082 1.383
8.00 712.20 1.037 1.181 704.79 1.056 1.270 697.34 1.072 1.361
9.00 713.05 1.029 1.162 705.68 1.048 1.250 698.30 1.063 1.340
10.00 713.88 1.020 1.144 706.56 1.039 1.230 699.23 1.054 1.319
10.99 714.70 1.012 1.127 707.43 1.030 1.212 700.16 1.045 1.299
12.00 715.51 1.003 1.110 708.29 1.021 1.193 701.08 1.036 1.279
13.00 716.30 0.995 1.093 709.14 1.013 1.175 701.98 1.028 1.259
14.00 717.10 0.987 1.077 709.98 1.005 1.157 702.87 1.019 1.240
15.00 717.87 0.979 1.060 710.81 0.997 1.140 703.75 1.011 1.221
16.00 718.64 0.972 1.045 711.62 0.989 1.123 704.61 1.003 1.203
17.00 719.39 0.964 1.030 712.43 0.981 1.106 705.47 0.995 1.185
18.00 720.16 0.956 1.015 713.25 0.973 1.090 706.33 0.987 1.168
19.00 720.88 0.949 1.000 714.01 0.966 1.074 707.13 0.979 1.151
20.00 721.61 0.942 0.986 714.78 0.958 1.059 707.94 0.972 1.134
21.00 722.32 0.935 0.972 715.55 0.951 1.044 708.75 0.964 1.118
22.00 723.02 0.927 0.958 716.30 0.943 1.029 709.53 0.957 1.102
23.00 723.68 0.921 0.944 716.98 0.936 1.014 710.30 0.949 1.086
24.00 724.32 0.914 0.931 717.65 0.929 1.000 711.03 0.942 1.071
25.00 724.92 0.907 0.918 718.30 0.922 0.986 711.74 0.935 1.056
T = 343.11 K T = 353.09 K T = 363.06 K
1.00 682.79 1.156 1.633 674.78 1.169 1.742 666.70 1.180 1.853
2.00 683.83 1.146 1.606 675.91 1.158 1.712 667.89 1.168 1.821
3.00 684.89 1.135 1.579 677.03 1.147 1.684 669.10 1.157 1.791
4.00 685.87 1.125 1.553 678.12 1.137 1.656 670.27 1.147 1.761
5.00 686.90 1.115 1.528 679.23 1.127 1.629 671.44 1.136 1.732
6.00 687.93 1.105 1.503 680.30 1.116 1.602 672.61 1.126 1.703
7.00 688.92 1.095 1.479 681.37 1.106 1.576 673.77 1.116 1.675
8.00 689.92 1.086 1.455 682.43 1.097 1.551 674.91 1.106 1.648
9.00 690.94 1.076 1.432 683.51 1.087 1.526 676.05 1.096 1.622
10.00 691.90 1.067 1.409 684.56 1.078 1.502 677.17 1.086 1.596
11.00 692.89 1.058 1.387 685.60 1.068 1.479 678.26 1.077 1.571
12.00 693.86 1.049 1.366 686.61 1.059 1.455 679.34 1.068 1.546
13.00 694.82 1.040 1.345 687.61 1.050 1.433 680.41 1.058 1.522
14.00 695.76 1.031 1.324 688.60 1.041 1.411 681.46 1.049 1.499
15.00 696.69 1.023 1.304 689.58 1.033 1.389 682.50 1.041 1.476
16.00 697.60 1.015 1.285 690.55 1.024 1.368 683.52 1.032 1.454
17.00 698.50 1.006 1.266 691.50 1.016 1.348 684.53 1.023 1.432
18.00 699.38 0.998 1.247 692.42 1.008 1.328 685.52 1.015 1.410
19.00 700.22 0.990 1.229 693.33 0.999 1.308 686.50 1.007 1.389
20.00 701.09 0.982 1.211 694.24 0.991 1.289 687.43 0.999 1.369
21.00 701.92 0.975 1.193 695.13 0.984 1.270 688.35 0.991 1.349
22.00 702.73 0.967 1.176 695.95 0.976 1.252 689.23 0.983 1.329
23.00 703.51 0.960 1.159 696.80 0.968 1.234 690.14 0.975 1.310
24.00 704.28 0.952 1.143 697.62 0.961 1.217 691.03 0.967 1.291
25.00 705.05 0.945 1.127 698.42 0.953 1.199 691.89 0.960 1.273
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.
138 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147

TABLE 6
Experimental densities for the binary mixture {n-heptane (1) + n-decane (2)} at x1 = 0.5219.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.18 K T = 323.14 K T = 333.11 K
1.00 695.19 1.148 1.420 687.21 1.177 1.535 679.05 1.202 1.654
2.00 696.01 1.136 1.394 688.12 1.165 1.507 680.06 1.190 1.624
3.00 696.84 1.125 1.369 689.02 1.154 1.480 681.02 1.178 1.594
4.00 697.74 1.115 1.345 689.95 1.142 1.453 682.02 1.167 1.566
5.00 698.60 1.104 1.321 690.88 1.132 1.427 683.02 1.155 1.538
6.00 699.50 1.093 1.298 691.82 1.121 1.402 684.02 1.144 1.511
7.00 700.44 1.083 1.275 692.78 1.110 1.378 685.02 1.133 1.484
8.00 701.28 1.073 1.253 693.71 1.100 1.354 686.03 1.123 1.458
9.00 702.17 1.063 1.232 694.65 1.090 1.331 687.04 1.112 1.433
10.00 703.05 1.054 1.211 695.58 1.080 1.308 688.03 1.102 1.409
10.99 703.90 1.044 1.191 696.50 1.070 1.287 689.01 1.092 1.385
12.00 704.76 1.035 1.171 697.40 1.060 1.265 689.97 1.082 1.362
13.00 705.60 1.026 1.152 698.29 1.051 1.244 690.92 1.072 1.339
14.00 706.44 1.017 1.133 699.17 1.041 1.223 691.85 1.062 1.317
15.00 707.25 1.008 1.115 700.04 1.032 1.204 692.77 1.053 1.295
16.00 708.05 0.999 1.097 700.90 1.023 1.184 693.68 1.044 1.274
17.00 708.84 0.991 1.079 701.74 1.014 1.165 694.58 1.034 1.254
18.00 709.64 0.982 1.062 702.60 1.006 1.147 695.49 1.026 1.234
19.00 710.37 0.974 1.046 703.38 0.997 1.129 696.33 1.017 1.214
20.00 711.12 0.966 1.029 704.18 0.989 1.111 697.15 1.008 1.195
21.00 711.85 0.958 1.014 704.97 0.981 1.094 697.97 1.000 1.176
22.00 712.53 0.950 0.998 705.70 0.972 1.077 698.76 0.991 1.158
23.00 713.24 0.943 0.983 706.43 0.964 1.060 699.54 0.983 1.140
24.00 713.92 0.935 0.968 707.14 0.957 1.044 700.30 0.975 1.123
25.00 714.55 0.927 0.954 707.83 0.949 1.029 701.04 0.967 1.106
T = 343.09 K T = 353.08 K T = 363.02 K
1.00 670.90 1.224 1.778 662.57 1.243 1.905 654.13 1.259 2.035
2.00 672.01 1.212 1.745 663.78 1.230 1.869 655.44 1.246 1.996
3.00 673.08 1.199 1.713 664.95 1.218 1.835 656.74 1.234 1.959
4.00 674.15 1.187 1.682 666.13 1.205 1.801 657.94 1.221 1.923
5.00 675.24 1.176 1.652 667.28 1.193 1.769 659.19 1.209 1.888
6.00 676.30 1.164 1.622 668.44 1.182 1.737 660.44 1.197 1.854
7.00 677.39 1.153 1.594 669.57 1.170 1.706 661.67 1.185 1.821
8.00 678.46 1.142 1.566 670.70 1.159 1.676 662.86 1.173 1.789
9.00 679.53 1.131 1.539 671.82 1.148 1.647 664.05 1.162 1.758
10.00 680.57 1.121 1.512 672.93 1.137 1.619 665.24 1.151 1.727
11.00 681.55 1.110 1.486 674.03 1.126 1.591 666.41 1.140 1.697
12.00 682.56 1.100 1.461 675.10 1.116 1.564 667.56 1.129 1.668
13.00 683.57 1.090 1.437 676.17 1.105 1.538 668.70 1.118 1.640
14.00 684.56 1.080 1.413 677.22 1.095 1.512 669.81 1.108 1.613
15.00 685.54 1.070 1.390 678.26 1.085 1.487 670.91 1.098 1.586
16.00 686.50 1.061 1.367 679.28 1.076 1.462 671.98 1.088 1.559
17.00 687.45 1.052 1.345 680.26 1.066 1.439 673.01 1.078 1.534
18.00 688.39 1.042 1.323 681.28 1.057 1.415 674.09 1.069 1.509
19.00 689.28 1.033 1.302 682.20 1.047 1.393 675.09 1.059 1.485
20.00 690.16 1.024 1.282 683.14 1.038 1.370 676.07 1.050 1.461
21.00 691.02 1.016 1.262 684.06 1.029 1.349 677.05 1.041 1.438
22.00 691.87 1.007 1.242 684.96 1.021 1.328 677.98 1.032 1.415
23.00 692.69 0.999 1.223 685.84 1.012 1.307 678.94 1.023 1.393
24.00 693.49 0.990 1.204 686.70 1.004 1.287 679.87 1.014 1.371
25.00 694.29 0.982 1.186 687.54 0.995 1.267 680.76 1.006 1.350
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.

TABLE 7
Experimental densities for the binary mixture {n-heptane (1) + n-decane (2)} at x1 = 0.7770.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.18 K T = 323.16 K T = 333.12 K
1.00 681.87 1.215 1.545 673.59 1.249 1.678 665.15 1.279 1.815
2.00 682.77 1.202 1.515 674.58 1.236 1.645 666.23 1.265 1.779
3.00 683.70 1.190 1.486 675.56 1.223 1.613 667.33 1.252 1.744
4.00 684.64 1.177 1.457 676.57 1.210 1.581 668.42 1.238 1.710
5.00 685.58 1.165 1.430 677.56 1.197 1.551 669.49 1.225 1.677
6.00 686.52 1.154 1.403 678.57 1.185 1.522 670.55 1.212 1.645
7.00 687.47 1.142 1.376 679.58 1.173 1.493 671.62 1.200 1.614
8.00 688.40 1.131 1.351 680.57 1.161 1.466 672.68 1.188 1.584
9.00 689.32 1.119 1.326 681.56 1.150 1.439 673.73 1.176 1.555
10.00 690.24 1.109 1.302 682.54 1.138 1.412 674.77 1.164 1.526
10.99 691.12 1.098 1.279 683.50 1.127 1.387 675.80 1.153 1.499
12.00 692.05 1.087 1.256 684.45 1.116 1.362 676.81 1.141 1.471
 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147 139

TABLE 7 (continued)

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
13.00 692.92 1.077 1.234 685.39 1.106 1.338 677.81 1.130 1.445
14.00 693.78 1.067 1.212 686.31 1.095 1.314 678.79 1.119 1.420
15.00 694.64 1.057 1.191 687.21 1.085 1.291 679.76 1.109 1.395
16.00 695.50 1.047 1.171 688.10 1.075 1.269 680.71 1.098 1.370
17.00 696.33 1.038 1.151 688.99 1.065 1.247 681.65 1.088 1.347
18.00 697.16 1.028 1.131 689.87 1.055 1.226 682.58 1.078 1.324
19.00 697.97 1.019 1.113 690.73 1.046 1.205 683.49 1.068 1.301
20.00 698.77 1.010 1.094 691.58 1.036 1.185 684.39 1.058 1.279
21.00 699.55 1.001 1.076 692.41 1.027 1.166 685.27 1.049 1.258
22.00 700.31 0.992 1.058 693.22 1.018 1.146 686.10 1.040 1.237
23.00 701.00 0.984 1.041 693.96 1.009 1.128 686.90 1.030 1.217
24.00 701.71 0.975 1.025 694.70 1.000 1.110 687.68 1.021 1.197
25.00 702.37 0.967 1.008 695.42 0.992 1.092 688.47 1.012 1.178
T = 343.09 K T = 353.08 K T = 363.02 K
1.00 656.56 1.305 1.957 647.84 1.328 2.104 639.00 1.348 2.255
2.00 657.76 1.291 1.918 649.19 1.313 2.062 640.47 1.333 2.209
3.00 658.95 1.277 1.880 650.47 1.299 2.021 641.89 1.318 2.165
4.00 660.13 1.263 1.843 651.73 1.284 1.981 643.28 1.303 2.122
5.00 661.28 1.249 1.808 653.01 1.271 1.942 644.65 1.289 2.080
6.00 662.42 1.236 1.773 654.25 1.257 1.905 646.00 1.275 2.040
7.00 663.56 1.223 1.739 655.46 1.244 1.868 647.32 1.262 2.001
8.00 664.71 1.211 1.707 656.67 1.231 1.833 648.61 1.248 1.962
9.00 665.84 1.198 1.675 657.88 1.218 1.799 649.89 1.235 1.925
10.00 666.95 1.186 1.644 659.06 1.206 1.765 651.15 1.222 1.889
11.00 668.04 1.174 1.614 660.22 1.194 1.733 652.39 1.210 1.854
12.00 669.13 1.163 1.584 661.36 1.182 1.701 653.61 1.198 1.820
13.00 670.20 1.151 1.556 662.49 1.170 1.670 654.81 1.186 1.787
14.00 671.24 1.140 1.528 663.61 1.158 1.640 655.99 1.174 1.755
15.00 672.27 1.129 1.501 664.70 1.147 1.611 657.15 1.162 1.724
16.00 673.29 1.119 1.475 665.77 1.136 1.583 658.24 1.151 1.693
17.00 674.28 1.108 1.450 666.82 1.125 1.555 659.41 1.140 1.663
18.00 675.26 1.098 1.425 667.86 1.115 1.528 660.50 1.129 1.634
19.00 676.22 1.088 1.400 668.89 1.104 1.502 661.57 1.118 1.606
20.00 677.14 1.078 1.377 669.88 1.094 1.477 662.62 1.108 1.579
21.00 678.06 1.068 1.354 670.85 1.084 1.452 663.64 1.098 1.552
22.00 678.95 1.058 1.331 671.79 1.074 1.428 664.64 1.087 1.526
23.00 679.82 1.049 1.309 672.72 1.064 1.404 665.63 1.078 1.500
24.00 680.67 1.039 1.288 673.63 1.055 1.381 666.60 1.068 1.476
25.00 681.49 1.030 1.267 674.52 1.045 1.358 667.53 1.058 1.451
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.

TABLE 8
Experimental densities for the binary mixture {n-heptane (1) + n-decane (2)} at x1 = 0.9520.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.17 K T = 323.14 K T = 333.13 K
1.00 671.13 1.264 1.652 662.62 1.304 1.803 653.95 1.339 1.960
2.00 672.16 1.250 1.616 663.72 1.289 1.764 655.14 1.323 1.918
3.00 673.18 1.235 1.582 664.82 1.274 1.726 656.33 1.307 1.877
4.00 674.17 1.221 1.549 665.90 1.259 1.690 657.51 1.292 1.837
5.00 675.18 1.208 1.517 666.98 1.245 1.655 658.67 1.277 1.798
6.00 676.18 1.194 1.486 668.05 1.231 1.620 659.82 1.263 1.761
7.00 677.15 1.181 1.456 669.10 1.217 1.587 660.95 1.249 1.724
8.00 678.12 1.169 1.426 670.14 1.204 1.555 662.06 1.235 1.689
9.00 679.08 1.156 1.398 671.16 1.191 1.524 663.16 1.221 1.655
10.00 680.03 1.144 1.370 672.17 1.178 1.494 664.24 1.208 1.622
10.99 680.95 1.132 1.344 673.16 1.166 1.465 665.30 1.195 1.590
12.00 681.86 1.120 1.318 674.14 1.153 1.436 666.34 1.182 1.559
13.00 682.77 1.109 1.292 675.10 1.141 1.408 667.37 1.170 1.529
14.00 683.65 1.097 1.268 676.05 1.130 1.381 668.38 1.158 1.499
15.00 684.52 1.086 1.244 676.99 1.118 1.355 669.39 1.146 1.471
16.00 685.39 1.076 1.221 677.91 1.107 1.330 670.37 1.134 1.443
17.00 686.24 1.065 1.198 678.82 1.096 1.305 671.33 1.123 1.416
18.00 687.08 1.055 1.177 679.71 1.085 1.281 672.29 1.111 1.390
19.00 687.90 1.044 1.155 680.59 1.074 1.258 673.23 1.101 1.365
20.00 688.71 1.034 1.135 681.45 1.064 1.235 674.14 1.090 1.340
21.00 689.52 1.025 1.114 682.30 1.054 1.213 675.04 1.079 1.316
22.00 690.29 1.015 1.095 683.13 1.044 1.192 675.93 1.069 1.292
23.00 691.05 1.005 1.076 683.92 1.034 1.171 676.79 1.059 1.270
24.00 691.82 0.996 1.057 684.73 1.024 1.150 677.64 1.049 1.247
25.00 692.57 0.987 1.039 685.51 1.015 1.131 678.45 1.039 1.226

(continued on next page)

140 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147

TABLE 8 (continued)

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1

T = 343.11 K T = 353.12 K T = 363.03 K

1.00 645.16 1.369 2.124 636.17 1.396 2.294 627.08 1.420 2.467
2.00 646.47 1.353 2.077 637.58 1.379 2.243 628.62 1.403 2.412
3.00 647.73 1.337 2.032 638.96 1.363 2.194 630.14 1.386 2.359
4.00 649.00 1.321 1.989 640.34 1.347 2.147 631.64 1.369 2.308
5.00 650.27 1.306 1.947 641.71 1.331 2.101 633.12 1.353 2.259
6.00 651.49 1.291 1.906 643.05 1.315 2.057 634.56 1.337 2.211
7.00 652.71 1.276 1.867 644.36 1.300 2.014 635.98 1.321 2.164
8.00 653.91 1.262 1.828 645.65 1.285 1.972 637.36 1.306 2.119
9.00 655.08 1.248 1.791 646.91 1.271 1.932 638.71 1.291 2.076
10.00 656.24 1.234 1.755 648.14 1.257 1.893 640.03 1.277 2.033
11.00 657.38 1.221 1.720 649.36 1.243 1.855 641.33 1.262 1.992
12.00 658.49 1.207 1.686 650.55 1.229 1.818 642.61 1.249 1.952
13.00 659.59 1.195 1.653 651.72 1.216 1.782 643.86 1.235 1.914
14.00 660.67 1.182 1.622 652.87 1.203 1.748 645.09 1.222 1.876
15.00 661.74 1.170 1.591 654.00 1.191 1.714 646.30 1.209 1.840
16.00 662.78 1.158 1.560 655.12 1.178 1.681 647.49 1.196 1.805
17.00 663.81 1.146 1.531 656.22 1.166 1.650 648.66 1.183 1.770
18.00 664.84 1.134 1.503 657.29 1.154 1.619 649.80 1.171 1.737
19.00 665.84 1.123 1.475 658.35 1.142 1.589 650.92 1.159 1.705
20.00 666.82 1.112 1.448 659.40 1.131 1.560 652.02 1.147 1.673
21.00 667.78 1.101 1.422 660.42 1.120 1.531 653.10 1.136 1.643
22.00 668.70 1.090 1.396 661.43 1.109 1.504 654.16 1.125 1.613
23.00 669.62 1.080 1.372 662.41 1.098 1.477 655.20 1.114 1.584
24.00 670.52 1.070 1.347 663.35 1.088 1.451 656.21 1.103 1.556
25.00 671.40 1.059 1.324 664.30 1.077 1.425 657.21 1.092 1.528
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.

TABLE 9
Experimental densities for the binary mixture {n-octane (1) + n-decane (2)} at x1 = 0.0616.a

p/MPa qm/kg  m3 ap  103/K1 jT  103/MPa1 qm/kg  m3 ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.14 K T = 323.19 K T = 333.12 K
1.00 714.37 1.068 1.252 706.61 1.089 1.351 698.91 1.107 1.451
2.00 715.15 1.058 1.231 707.46 1.079 1.328 699.91 1.097 1.427
3.00 716.00 1.049 1.211 708.43 1.070 1.306 700.87 1.087 1.403
4.00 716.89 1.040 1.191 709.27 1.060 1.284 701.83 1.077 1.380
5.00 717.71 1.030 1.171 710.19 1.051 1.263 702.77 1.068 1.357
6.00 718.51 1.022 1.152 711.06 1.042 1.243 703.69 1.058 1.335
7.00 719.36 1.013 1.134 711.94 1.033 1.223 704.67 1.049 1.313
8.00 720.16 1.004 1.116 712.81 1.024 1.203 705.56 1.040 1.292
9.00 720.97 0.996 1.099 713.68 1.015 1.184 706.45 1.031 1.272
10.00 721.75 0.987 1.081 714.53 1.006 1.166 707.38 1.022 1.251
10.99 722.52 0.979 1.065 715.36 0.998 1.148 708.26 1.013 1.232
12.00 723.27 0.971 1.048 716.18 0.990 1.130 709.09 1.005 1.213
13.00 724.05 0.963 1.032 716.99 0.981 1.113 709.96 0.996 1.194
14.00 724.81 0.955 1.017 717.79 0.973 1.096 710.80 0.988 1.176
15.00 725.50 0.948 1.001 718.57 0.965 1.079 711.63 0.980 1.158
16.00 726.26 0.940 0.986 719.34 0.958 1.063 712.43 0.972 1.140
17.00 726.99 0.933 0.972 720.12 0.950 1.047 713.28 0.964 1.123
18.00 727.69 0.925 0.958 720.90 0.942 1.032 714.06 0.957 1.107
19.00 728.37 0.918 0.944 721.64 0.935 1.016 714.88 0.949 1.090
20.00 729.06 0.911 0.930 722.37 0.928 1.002 715.65 0.941 1.074
21.00 729.73 0.904 0.916 723.09 0.921 0.987 716.44 0.934 1.059
22.00 730.38 0.897 0.903 723.78 0.914 0.973 717.15 0.927 1.044
23.00 731.03 0.890 0.891 724.44 0.907 0.959 717.89 0.920 1.029
24.00 731.60 0.884 0.878 725.08 0.900 0.946 718.59 0.913 1.014
25.00 732.22 0.877 0.866 725.73 0.893 0.932 719.30 0.906 1.000
T = 343.11 K T = 353.12 K T = 363.03 K
1.00 691.23 1.122 1.555 683.44 1.135 1.661 675.72 1.146 1.769
2.00 692.25 1.112 1.528 684.54 1.124 1.633 676.86 1.135 1.739
3.00 693.27 1.102 1.503 685.62 1.114 1.605 678.03 1.124 1.709
4.00 694.28 1.092 1.478 686.69 1.104 1.578 679.17 1.114 1.680
5.00 695.27 1.082 1.453 687.76 1.094 1.552 680.28 1.103 1.652
6.00 696.28 1.072 1.430 688.82 1.084 1.527 681.38 1.093 1.625
7.00 697.25 1.063 1.406 689.85 1.074 1.502 682.50 1.083 1.598
8.00 698.24 1.053 1.383 690.88 1.064 1.477 683.60 1.074 1.572
9.00 699.21 1.044 1.361 691.90 1.055 1.453 684.68 1.064 1.546
10.00 700.15 1.035 1.340 692.88 1.046 1.430 685.70 1.055 1.522
10.99 701.09 1.026 1.319 693.88 1.037 1.408 686.75 1.045 1.497
12.00 702.04 1.017 1.298 694.85 1.028 1.386 687.80 1.036 1.474
13.00 702.94 1.009 1.278 695.80 1.019 1.364 688.75 1.027 1.451
 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147 141

TABLE 9 (continued)

p/MPa qm/kg  m3 ap  103/K1 jT  103/MPa1 qm/kg  m3 ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
14.00 703.83 1.000 1.258 696.76 1.010 1.343 689.77 1.019 1.428
15.00 704.71 0.992 1.239 697.70 1.002 1.322 690.77 1.010 1.406
16.00 705.59 0.984 1.220 698.61 0.994 1.302 691.73 1.002 1.384
17.00 706.44 0.976 1.202 699.52 0.986 1.282 692.68 0.993 1.363
18.00 707.29 0.968 1.184 700.43 0.978 1.263 693.63 0.985 1.343
19.00 708.13 0.960 1.167 701.32 0.970 1.244 694.55 0.977 1.323
20.00 708.97 0.953 1.149 702.19 0.962 1.226 695.46 0.969 1.303
21.00 709.77 0.945 1.132 703.05 0.954 1.208 696.37 0.961 1.284
22.00 710.54 0.938 1.116 703.89 0.947 1.190 697.23 0.954 1.265
23.00 711.34 0.930 1.100 704.72 0.939 1.173 698.12 0.946 1.247
24.00 712.11 0.923 1.084 705.52 0.932 1.156 699.00 0.939 1.229
25.00 712.86 0.916 1.069 706.29 0.925 1.140 699.81 0.931 1.211
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.

TABLE 10
Experimental densities for the binary mixture {n-octane (1) + n-decane (2)} at x1 = 0.2801.a

p/MPa qm/kg  m3 ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/kg  m3 ap  103/K1 jT  103/MPa1
T = 313.17 K T = 323.13 K T = 333.12 K
1.00 709.26 1.086 1.294 701.50 1.108 1.393 693.73 1.128 1.496
2.00 710.07 1.076 1.272 702.42 1.098 1.370 694.68 1.118 1.471
3.00 710.90 1.066 1.251 703.33 1.089 1.347 695.65 1.107 1.447
4.00 711.79 1.057 1.230 704.26 1.079 1.325 696.63 1.097 1.423
5.00 712.65 1.048 1.210 705.16 1.069 1.303 697.61 1.088 1.399
6.00 713.47 1.039 1.191 706.06 1.060 1.282 698.55 1.078 1.376
7.00 714.32 1.030 1.172 706.95 1.051 1.261 699.50 1.069 1.354
8.00 715.17 1.021 1.153 707.83 1.042 1.241 700.43 1.059 1.332
9.00 715.99 1.012 1.135 708.70 1.033 1.222 701.36 1.050 1.311
10.00 716.81 1.004 1.117 709.57 1.024 1.203 702.27 1.041 1.291
10.99 717.63 0.995 1.100 710.50 1.015 1.183 703.19 1.032 1.270
12.00 718.42 0.987 1.083 711.29 1.007 1.166 704.10 1.024 1.251
13.00 719.20 0.979 1.067 712.12 0.999 1.148 704.98 1.015 1.231
14.00 719.98 0.971 1.051 712.97 0.990 1.130 705.81 1.007 1.213
15.00 720.74 0.963 1.035 713.78 0.982 1.113 706.72 0.998 1.194
16.00 721.50 0.956 1.019 714.58 0.974 1.097 707.59 0.990 1.176
17.00 722.23 0.948 1.004 715.38 0.967 1.080 708.43 0.982 1.159
18.00 723.00 0.940 0.990 716.14 0.959 1.064 709.25 0.974 1.141
19.00 723.67 0.933 0.975 716.90 0.951 1.049 710.06 0.967 1.125
20.00 724.35 0.926 0.961 717.66 0.944 1.033 710.83 0.959 1.108
21.00 725.02 0.919 0.947 718.38 0.937 1.019 711.62 0.951 1.092
22.00 725.70 0.912 0.934 719.06 0.929 1.004 712.40 0.944 1.076
23.00 726.30 0.905 0.920 719.71 0.922 0.990 713.12 0.937 1.061
24.00 726.90 0.898 0.908 720.38 0.915 0.976 713.84 0.930 1.046
25.00 727.55 0.891 0.895 721.00 0.908 0.962 714.53 0.923 1.031
T = 343.12 K T = 353.12 K T = 363.05 K
1.00 686.00 1.145 1.602 678.06 1.159 1.711 670.18 1.171 1.822
2.00 686.96 1.134 1.575 679.14 1.148 1.682 671.39 1.159 1.790
3.00 688.00 1.124 1.549 680.24 1.137 1.653 672.48 1.148 1.760
4.00 689.01 1.113 1.523 681.31 1.127 1.626 673.67 1.138 1.730
5.00 690.04 1.103 1.498 682.40 1.116 1.599 674.81 1.127 1.701
6.00 691.09 1.093 1.473 683.48 1.106 1.572 675.97 1.117 1.673
7.00 692.03 1.084 1.449 684.52 1.096 1.547 677.07 1.107 1.645
8.00 693.02 1.074 1.426 685.57 1.086 1.522 678.19 1.097 1.619
9.00 694.00 1.065 1.403 686.58 1.077 1.497 679.28 1.087 1.592
10.00 694.95 1.055 1.381 687.61 1.067 1.473 680.35 1.077 1.567
10.99 695.95 1.046 1.359 688.64 1.058 1.450 681.42 1.068 1.542
12.00 696.90 1.037 1.338 689.64 1.049 1.427 682.49 1.059 1.518
13.00 697.84 1.029 1.317 690.64 1.040 1.405 683.53 1.050 1.494
14.00 698.78 1.020 1.297 691.60 1.031 1.383 684.56 1.041 1.471
15.00 699.72 1.012 1.277 692.59 1.023 1.362 685.57 1.032 1.448
16.00 700.60 1.003 1.258 693.55 1.014 1.341 686.57 1.023 1.426
17.00 701.51 0.995 1.239 694.46 1.006 1.321 687.56 1.015 1.404
18.00 702.35 0.987 1.220 695.35 0.998 1.301 688.51 1.006 1.383
19.00 703.17 0.979 1.202 696.27 0.990 1.282 689.47 0.998 1.362
20.00 704.02 0.971 1.185 697.16 0.982 1.263 690.38 0.990 1.342
21.00 704.83 0.964 1.167 698.02 0.974 1.244 691.33 0.982 1.322
22.00 705.63 0.956 1.150 698.88 0.966 1.226 692.19 0.974 1.303
23.00 706.41 0.949 1.134 699.72 0.958 1.208 693.06 0.966 1.284
24.00 707.17 0.941 1.118 700.52 0.951 1.191 693.94 0.959 1.265
25.00 707.92 0.934 1.102 701.34 0.944 1.174 694.78 0.951 1.247
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.
142 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147

bridge (Model F300, ARK). The pressure transducer was calibrated again degassed as well as the lighter compound from its autoclave.
against a dead weight balance (DH Instruments, model 5304). Finally it was introduced into the loading cell, which has the first
Combined uncertainties were ±0.03 K for temperature, ±0.02 MPa compound without air, and weighed. The composition of the mix-
for pressure. ture was obtained by the difference of each mass registered in the
aforementioned stages with an estimated uncertainty of ±1  104
2.3. Density measurements mole fraction.
Furthermore, the loading cell was placed inside the oven; all the
Water and nitrogen were used as reference fluids to calibrate circuit where the mixture and nitrogen flows and densimeter were
the VTD as described elsewhere [21,22]. Known composition of degassed. The stirring system was turned on; the oven and circu-
each binary n-alkane mixture was carefully prepared by successive lating liquid bath were set to the initial desired condition
weightings [23] using a comparator balance (Sartorius, MCA 1200). (T = 313 K). After waiting for about 50 min, the loading valve was
Chemicals were located in separate autoclave and connected on- opened for allowing the homogeneous mixture flows to the
line through needle valves to the loading cell. It started with the densimeter. Next, the automatic data acquisition was turned on
degassing of all the tubing circuit and the heavier compounds by to obtain a better data register and criterion related to the stabil-
a vacuum pump. Then, this was transferred to the empty loading ization of the variables. It was considered when values of the three
cell and weighed to determine its mass. The tubing circuit was variables changed within the uncertainty of each instrument.

TABLE 11
Experimental densities for the binary mixture {n-octane (1) + n-decane (2)} at x1 = 0.5314.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.19 K T = 323.15 K T = 333.13 K
1.00 702.80 1.123 1.350 694.85 1.143 1.461 686.94 1.160 1.576
2.00 703.69 1.112 1.326 695.78 1.132 1.435 687.94 1.149 1.547
3.00 704.53 1.101 1.302 696.73 1.121 1.409 688.95 1.137 1.519
4.00 705.35 1.091 1.279 697.62 1.110 1.384 689.94 1.126 1.492
5.00 706.16 1.080 1.256 698.58 1.099 1.359 690.92 1.115 1.466
6.00 707.05 1.070 1.234 699.53 1.089 1.336 691.92 1.105 1.440
7.00 707.93 1.060 1.213 700.45 1.079 1.312 692.89 1.094 1.415
8.00 708.77 1.051 1.192 701.36 1.069 1.290 693.87 1.084 1.390
9.00 709.59 1.041 1.172 702.24 1.059 1.268 694.82 1.074 1.366
10.00 710.43 1.032 1.152 703.12 1.049 1.246 695.75 1.064 1.343
10.99 711.26 1.023 1.133 703.99 1.040 1.226 696.68 1.054 1.320
12.00 712.06 1.013 1.114 704.86 1.031 1.205 697.60 1.045 1.298
13.00 712.86 1.005 1.096 705.72 1.021 1.185 698.50 1.035 1.277
14.00 713.65 0.996 1.078 706.56 1.012 1.166 699.40 1.026 1.256
15.00 714.44 0.987 1.061 707.39 1.004 1.147 700.28 1.017 1.235
16.00 715.21 0.979 1.044 708.22 0.995 1.129 701.15 1.008 1.215
17.00 715.97 0.971 1.027 709.02 0.986 1.110 702.00 1.000 1.196
18.00 716.73 0.962 1.011 709.85 0.978 1.093 702.88 0.991 1.177
19.00 717.47 0.954 0.995 710.62 0.970 1.076 703.68 0.983 1.158
20.00 718.20 0.946 0.980 711.38 0.962 1.059 704.48 0.974 1.140
21.00 718.89 0.939 0.965 712.12 0.954 1.043 705.27 0.966 1.122
22.00 719.56 0.931 0.950 712.85 0.946 1.027 706.05 0.958 1.105
23.00 720.23 0.923 0.936 713.54 0.938 1.011 706.81 0.950 1.088
24.00 720.88 0.916 0.922 714.24 0.931 0.996 707.53 0.943 1.072
25.00 721.52 0.909 0.908 714.88 0.923 0.981 708.26 0.935 1.055
T = 343.12 K T = 353.12 K T = 363.02 K
1.00 678.98 1.175 1.694 670.91 1.187 1.815 662.89 1.197 1.937
2.00 680.05 1.163 1.663 672.10 1.175 1.781 664.16 1.185 1.901
3.00 681.13 1.151 1.632 673.23 1.163 1.748 665.39 1.173 1.865
4.00 682.20 1.140 1.603 674.37 1.151 1.717 666.61 1.161 1.832
5.00 683.26 1.129 1.574 675.52 1.140 1.686 667.85 1.149 1.798
6.00 684.32 1.118 1.546 676.65 1.129 1.656 669.05 1.138 1.766
7.00 685.36 1.107 1.519 677.77 1.118 1.627 670.24 1.127 1.735
8.00 686.38 1.097 1.493 678.86 1.107 1.598 671.39 1.116 1.704
9.00 687.39 1.086 1.467 679.93 1.097 1.570 672.53 1.105 1.674
10.00 688.38 1.076 1.442 680.99 1.086 1.543 673.66 1.094 1.645
10.99 689.37 1.066 1.418 682.03 1.076 1.517 674.79 1.084 1.617
12.00 690.34 1.057 1.394 683.07 1.066 1.491 675.87 1.074 1.590
13.00 691.29 1.047 1.371 684.09 1.057 1.466 676.95 1.064 1.563
14.00 692.24 1.038 1.348 685.09 1.047 1.442 678.01 1.054 1.537
15.00 693.17 1.028 1.326 686.08 1.038 1.418 679.06 1.045 1.511
16.00 694.09 1.019 1.304 687.05 1.028 1.395 680.09 1.035 1.486
17.00 695.00 1.010 1.283 688.00 1.019 1.373 681.10 1.026 1.462
18.00 695.89 1.002 1.263 688.93 1.010 1.350 682.10 1.017 1.439
19.00 696.76 0.993 1.243 689.85 1.002 1.329 683.10 1.008 1.415
20.00 697.62 0.985 1.223 690.77 0.993 1.308 684.05 0.999 1.393
21.00 698.47 0.976 1.204 691.66 0.985 1.287 685.00 0.991 1.371
22.00 699.29 0.968 1.185 692.54 0.976 1.267 685.91 0.982 1.349
23.00 700.11 0.960 1.167 693.39 0.968 1.248 686.82 0.974 1.329
24.00 700.89 0.952 1.149 694.23 0.960 1.229 687.69 0.966 1.308
25.00 701.69 0.944 1.132 695.07 0.952 1.210 688.57 0.958 1.288
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1 Expanded
uncertainty U is U(qm) = 0.19 kg  m3.
 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147 143

TABLE 12
Experimental densities for the binary mixture {n-octane (1) + n-decane (2)} at x1 = 0.7736.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1
T = 313.19 K T = 323.15 K T = 333.14 K
1.00 695.32 1.146 1.412 687.38 1.170 1.527 679.32 1.191 1.645
2.00 696.27 1.134 1.387 688.41 1.158 1.499 680.38 1.179 1.615
3.00 697.14 1.123 1.362 689.33 1.147 1.472 681.42 1.167 1.586
4.00 698.01 1.113 1.338 690.27 1.136 1.446 682.44 1.156 1.558
5.00 698.89 1.102 1.315 691.21 1.125 1.420 683.46 1.144 1.530
6.00 699.80 1.092 1.292 692.18 1.114 1.395 684.50 1.133 1.503
7.00 700.67 1.082 1.269 693.12 1.104 1.371 685.49 1.123 1.476
8.00 701.55 1.072 1.248 694.08 1.093 1.348 686.50 1.112 1.451
9.00 702.44 1.062 1.227 694.99 1.083 1.325 687.47 1.102 1.426
10.00 703.28 1.052 1.206 695.89 1.073 1.302 688.42 1.091 1.402
10.99 704.16 1.043 1.186 696.80 1.064 1.280 689.42 1.081 1.378
12.00 705.00 1.034 1.166 697.73 1.054 1.259 690.37 1.072 1.355
13.00 705.81 1.024 1.147 698.56 1.045 1.238 691.27 1.062 1.333
14.00 706.63 1.015 1.128 699.43 1.036 1.218 692.21 1.052 1.311
15.00 707.47 1.007 1.110 700.30 1.026 1.198 693.10 1.043 1.289
16.00 708.28 0.998 1.092 701.16 1.018 1.179 694.02 1.034 1.268
17.00 709.10 0.990 1.075 702.00 1.009 1.160 694.90 1.025 1.248
18.00 709.83 0.981 1.058 702.81 1.000 1.142 695.77 1.016 1.228
19.00 710.61 0.973 1.041 703.60 0.992 1.124 696.62 1.008 1.209
20.00 711.34 0.965 1.025 704.40 0.983 1.106 697.46 0.999 1.190
21.00 712.07 0.957 1.009 705.18 0.975 1.089 698.28 0.991 1.171
22.00 712.79 0.949 0.994 705.95 0.967 1.072 699.09 0.982 1.153
23.00 713.47 0.941 0.979 706.68 0.959 1.056 699.86 0.974 1.135
24.00 714.14 0.934 0.964 707.39 0.952 1.040 700.61 0.966 1.118
25.00 714.77 0.926 0.950 708.08 0.944 1.024 701.34 0.958 1.101
T = 343.12 K T = 353.12 K T = 363.07 K
1.00 671.23 1.208 1.767 663.00 1.224 1.891 654.79 1.237 2.018
2.00 672.36 1.196 1.734 664.25 1.211 1.857 656.13 1.224 1.981
3.00 673.44 1.184 1.703 665.41 1.199 1.822 657.39 1.211 1.945
4.00 674.54 1.172 1.672 666.60 1.187 1.789 658.68 1.199 1.909
5.00 675.64 1.161 1.642 667.77 1.175 1.757 659.92 1.187 1.875
6.00 676.76 1.150 1.613 668.95 1.163 1.726 661.18 1.175 1.841
7.00 677.83 1.138 1.584 670.08 1.152 1.695 662.38 1.163 1.808
8.00 678.88 1.128 1.557 671.21 1.141 1.665 663.57 1.152 1.776
9.00 679.92 1.117 1.530 672.31 1.130 1.637 664.75 1.141 1.745
10.00 680.93 1.107 1.504 673.43 1.119 1.608 665.92 1.130 1.715
10.99 681.98 1.096 1.478 674.52 1.109 1.581 667.06 1.119 1.686
12.00 682.98 1.086 1.453 675.55 1.099 1.554 668.19 1.109 1.657
13.00 683.94 1.076 1.429 676.59 1.088 1.528 669.32 1.098 1.629
14.00 684.91 1.067 1.405 677.61 1.079 1.503 670.41 1.088 1.602
15.00 685.89 1.057 1.382 678.66 1.069 1.478 671.49 1.078 1.575
16.00 686.84 1.048 1.360 679.66 1.059 1.454 672.56 1.069 1.549
17.00 687.80 1.039 1.338 680.68 1.050 1.430 673.60 1.059 1.524
18.00 688.72 1.030 1.317 681.63 1.041 1.407 674.63 1.050 1.499
19.00 689.61 1.021 1.296 682.58 1.032 1.384 675.61 1.040 1.475
20.00 690.48 1.012 1.275 683.51 1.023 1.363 676.63 1.031 1.451
21.00 691.35 1.003 1.255 684.41 1.014 1.341 677.57 1.022 1.428
22.00 692.20 0.995 1.236 685.32 1.005 1.320 678.47 1.014 1.406
23.00 693.03 0.987 1.217 686.21 0.997 1.300 679.43 1.005 1.384
24.00 693.84 0.978 1.198 687.06 0.988 1.280 680.34 0.997 1.365
25.00 694.61 0.970 1.180 687.92 0.980 1.260 681.28 0.988 1.342
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K; u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.

Isothermal measurements started at the lowest temperature which relates the vibrating period of the fluid sF, water sH2 O and
and pressure (313 K and 1 MPa) with pressure increments of nitrogen sN2 to the density of water qH2 O and nitrogen qN2 . Densities
1 MPa up to reach the maximum pressure of 25 MPa. The T, p for these reference fluids were obtained from the equations pro-
and vibrating period of the mixture sF were registered after the sta- posed by Wagner and Prub [25] and Span et al. [26], respectively.
bilization of the variables at each pressure. The next temperatures
were fixed with increments of 10 K and the same procedure was
3. Results and discussion
again followed. The expanded uncertainty (k = 2) for density was
estimated within 0.19 kg  m3. It was computed according to the
Experimental densities of high purity compounds and binary
recommended NIST procedure [24].
mixtures were measured at constant temperature and pressures
Finally, the density of the pure compound or the mixture at a
from (1 to 25) MPa. In order to check for the performance of the
fixed composition, temperature and pressure was calculated using
vibrating tube densimeter, densities of n-heptane and n-decane
the following equation:
were obtained at T = (313.18, 333.04, and 353.06) K; and from
qF ðp; T; sÞ ¼ qH2 O ðp; TÞþ (313 to 363) K in temperature intervals of 10 K, respectively. These
½s2F ðp; TÞ  s2H2 O ðp; TÞ ½qH2 O ðp; TÞ  qN2 ðp; TÞ values are reported in tables 2 and 3.
; ð1Þ Experimental densities for n-heptane were compared with
s2H2 O ðp; TÞ  s2N2 ðp; TÞ those calculated by the proposed equation by Schilling et al.
144 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147

[27] whose claim for an uncertainty of ±0.02%. Percentage devi- c3  ðc4 =T þ c5 =T 1=3 Þ þ p
ations are shown in figure 2. This equation provided a suitable qm ¼ : ð2Þ
c1 þ c2 p
correlation for densities over a wide range of temperature and
pressure. Taking into account our experimental uncertainty Densities for n-decane measured in this work were compared
and the deviation for this equation, good agreement was against the thermophysics data available at NIST [31]. These are de-
achieved for our densities. Additional tests were performed with rived from the equation reported by Lemmon and Span [32] whose
the aim of confirming the reliability of the source equation. present 0.2% of uncertainty. As can be observed in figure 3, devia-
Data from table 2 were fitted to the five-parameter equation tions between both sets of data are lower than 0.07%; therefore, it
(MTS) [28] and the calculated values were compared with the is assumed that the experimental results are acceptable. Densities
experimental sets of data published by Schilling et al. [27] presented in table 3 are also in agreement with those experimental
and Berge et al. [29] that were within the temperature and values from references [28,33,34]. These were compared by corre-
pressure range of the present study. The comparison demon- lating our results with equation (2). Density uncertainties for the
strated satisfactory results for the density data within both reference data [28,33,34] were claimed to be ±0.2 kg  m3, ±0.2%
uncertainties. and ±0.7 kg  m3 in that order.
The MTS equation is a modification from the original proposed Densities of the two binary n-alkane systems were measured
by Toscani-Szwarc [30] and is expressed according to: isothermally from (313 to 363) K and pressures up to 25 MPa

TABLE 13
Experimental densities for the binary mixture {n-octane (1) + n-decane (2)} at x1 = 0.9623.a

p/MPa qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 jT  103/MPa1 qm/(kg  m3) ap  103/K1 /MPa1
T = 313.17 K T = 323.15 K T = 333.13 K
1.00 688.85 1.163 1.479 680.80 1.191 1.599 672.68 1.215 1.723
2.00 689.77 1.151 1.452 681.80 1.179 1.569 673.73 1.203 1.691
3.00 690.64 1.140 1.425 682.74 1.167 1.540 674.77 1.191 1.660
4.00 691.53 1.129 1.399 683.68 1.155 1.512 675.80 1.179 1.629
5.00 692.37 1.118 1.374 684.65 1.144 1.485 676.82 1.167 1.599
6.00 693.31 1.107 1.349 685.60 1.133 1.458 677.85 1.155 1.570
7.00 694.24 1.096 1.326 686.57 1.122 1.432 678.88 1.144 1.542
8.00 695.11 1.086 1.302 687.54 1.111 1.407 679.95 1.133 1.515
9.00 696.04 1.076 1.279 688.50 1.101 1.382 680.98 1.122 1.488
10.00 696.93 1.066 1.257 689.46 1.090 1.358 681.98 1.111 1.462
10.99 697.85 1.056 1.236 690.40 1.080 1.335 682.99 1.101 1.437
12.00 698.72 1.046 1.215 691.34 1.070 1.312 683.98 1.091 1.412
13.00 699.57 1.037 1.194 692.26 1.060 1.290 684.93 1.081 1.388
14.00 700.45 1.027 1.174 693.16 1.051 1.268 685.89 1.071 1.365
15.00 701.33 1.018 1.155 694.06 1.041 1.247 686.87 1.061 1.342
16.00 702.18 1.009 1.136 694.94 1.032 1.226 687.76 1.051 1.319
17.00 703.00 1.001 1.118 695.80 1.023 1.206 688.67 1.042 1.298
18.00 703.81 0.992 1.100 696.65 1.014 1.187 689.57 1.033 1.276
19.00 704.60 0.983 1.082 697.48 1.005 1.167 690.49 1.024 1.256
20.00 705.32 0.975 1.065 698.30 0.997 1.149 691.35 1.015 1.236
21.00 706.06 0.967 1.048 699.10 0.988 1.131 692.18 1.006 1.216
22.00 706.80 0.959 1.032 699.83 0.980 1.113 693.00 0.998 1.197
23.00 707.48 0.951 1.015 700.57 0.972 1.095 693.78 0.989 1.178
24.00 708.16 0.943 1.000 701.31 0.964 1.079 694.55 0.981 1.160
25.00 708.78 0.935 0.985 702.00 0.956 1.062 695.28 0.973 1.142
T = 343.13 K T = 353.08 K T = 363.07 K
1.00 664.48 1.236 1.851 656.17 1.255 1.983 647.67 1.270 2.118
2.00 665.59 1.224 1.817 657.39 1.241 1.945 649.03 1.257 2.077
3.00 666.77 1.211 1.783 658.62 1.228 1.908 650.38 1.243 2.038
4.00 667.86 1.199 1.749 659.85 1.216 1.873 651.70 1.230 2.000
5.00 668.95 1.186 1.717 660.99 1.203 1.838 652.98 1.218 1.962
6.00 670.06 1.175 1.686 662.16 1.191 1.804 654.25 1.205 1.926
7.00 671.17 1.163 1.656 663.38 1.179 1.772 655.52 1.193 1.891
8.00 672.27 1.152 1.626 664.55 1.167 1.740 656.76 1.181 1.857
9.00 673.35 1.140 1.597 665.71 1.156 1.709 658.00 1.169 1.823
10.00 674.41 1.129 1.569 666.85 1.145 1.678 659.23 1.158 1.791
10.99 675.48 1.119 1.542 667.94 1.134 1.649 660.42 1.147 1.759
12.00 676.54 1.108 1.515 669.10 1.123 1.620 661.58 1.136 1.729
13.00 677.56 1.098 1.489 670.16 1.112 1.592 662.75 1.125 1.699
14.00 678.58 1.088 1.464 671.22 1.102 1.565 663.87 1.114 1.669
15.00 679.60 1.078 1.439 672.32 1.092 1.539 664.99 1.104 1.641
16.00 680.56 1.068 1.415 673.37 1.082 1.513 666.07 1.093 1.613
17.00 681.54 1.058 1.392 674.40 1.072 1.488 667.17 1.083 1.586
18.00 682.46 1.049 1.369 675.38 1.062 1.463 668.20 1.073 1.560
19.00 683.41 1.040 1.347 676.37 1.053 1.439 669.26 1.064 1.534
20.00 684.31 1.030 1.325 677.30 1.043 1.416 670.29 1.054 1.509
21.00 685.19 1.021 1.304 678.26 1.034 1.393 671.30 1.045 1.485
22.00 686.05 1.013 1.283 679.19 1.025 1.371 672.27 1.036 1.461
23.00 686.90 1.004 1.263 680.04 1.016 1.349 673.14 1.027 1.437
24.00 687.72 0.995 1.243 680.91 1.008 1.328 674.08 1.018 1.415
25.00 688.50 0.987 1.224 681.75 0.999 1.307 674.98 1.009 1.393
a
Standard uncertainties u are u(x) = 1  104 mol per mol, u(T) = 0.03 K, u(p) = 0.02 MPa, u(qm) = 0.095 kg  m3, u(ap) = 1.2  107 K1, u(jT) = 1.9  106 MPa1. Expanded
uncertainty U is U(qm) = 0.19 kg  m3.
 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147 145

covering the entire range of composition. The compositions for the The excess molar volumes for both binary systems exhibit the
{n-heptane (1) + n-decane (2)} mixtures were prepared at maximum negative values from ideality at about the equimolar
x1 = (0.0531, 0.2594, 0.5219, 0.777, and 0.952). Experimental data sample; therefore the deviation is symmetrical.
are reported in tables 4 to 8. Densities for the corresponding {n-oc- For the (n-heptane + n-decane) system, this variable reaches po-
tane (1) + n-decane (2)} mixtures are listed in tables 9 to 13 at sitive values at low compositions of the heavy compound within
compositions of x1 = (0.0616, 0.2801, 0.5314, 0.7736, and 0.9623). the range T = (313 to 343) K. Due to fact that the VE values show
Density behaviour for the two binary n-alkane systems was the same behaviour for the intermediate temperatures and are
proportional to pressure changes at fixed composition and temper- within the values reported at T = (313 and 363) K, an example of
ature. In contrast, this property decreased as temperature in- the temperature and pressure dependence for VE is plotted in fig-
creased for all pressures and compositions. ure 4. The excess molar volume data tend to be high negative as
Excess molar volumes VE were calculated with equation (3). temperature increases at constant pressure. For pressure changes
  at fixed temperature, lower deviations from ideality are gathered
x1 M1 þ ð1  x1 ÞM2 x1 M 1 ð1  x1 ÞM 2
VE ¼  þ : ð3Þ as pressure increases. However these trends are slightly different
qm q1 q2 for the (n-octane + n-decane) as shown in figure 5. The deviations
It is a function of the mixture density qm, molar mass M and mole from ideality are negative for the intermediate mixtures; these
fraction x, subscripts 1 and 2 denote each compound of the binary change to show positive behaviour at diluted compositions of both
mixture. Densities for each pure component (q1, q2) were calcu- components.
lated from reference equations [27,32,35]. According to the declared uncertainty for the excess molar vol-
The combined uncertainty was calculated according to equation umes obtained, the positive values at low and high compositions
(3) and was estimated to be ± 8.5  105 m3  kmol1. with respect to light component could reach zero or negative.

FIGURE 4. Plot of excess molar volumes VE against mole fraction for the {n-heptane FIGURE 6. Temperature and pressure dependence for the isobaric thermal expan-
(1) + n-decane (2)} system at: (d, s) 1 MPa, (., r) 15 MPa, (j, h) 25 MPa. Black sivity ap in the {n-heptane (1) + n-decane (2)} system at: (d, s) 1 MPa, (., 5)
and open symbols denote T  313 K and T  363 K, respectively. Trends are denoted 15 MPa, (j, h) 25 MPa. Black and open symbols denote T  313 K and T  363 K, in
by dashed and solid and lines. that order.

FIGURE 5. Plot of excess molar volumes VE against mole fraction for the {n-octane FIGURE 7. Temperature and pressure dependence for the isothermal compress-
(1) + n-decane (2)} system at: (d, s) 1 MPa, (., 5)15 MPa, (j, h) 25 MPa. Black and ibility jT in the {n-heptane (1) + n-decane (2)} system at: (d, s) 1 MPa, (., 5)
open symbols denote T  313 K and T  363 K, respectively. Trends are denoted by 15 MPa, (j, h) 25 MPa. Black and open symbols denote T  313 K and T  363 K, in
dashed and solid and lines. that order.
146 R. Quevedo-Nolasco et al. / J. Chem. Thermodynamics 44 (2012) 133–147

TABLE 14
Parameters for the modified Toscani–Szwarc (MTS) equation.

x1 c1/(MPa  m3  kg1) c2/(m3  kg1) c3/MPa c4/(K  MPa) c5/(K1/3  MPa)

n-Heptane (1)
1.000 0.13707 1.2633  103 212.315 29921.14 2711.04
n-Decane (1)
1.000 0.16487 1.1907  103 162.387 24927.07 2443.31
{n-Heptane (1) + n-decane (2)}
0.0531 0.16000 1.1965  103 208.655 32504.61 2894.04
0.2594 0.15607 1.2082  103 193.091 29449.43 2697.21
0.5219 0.14427 1.2325  103 209.003 31333.23 2778.62
0.7770 0.13590 1.2552  103 216.581 31682.72 2785.88
0.9520 0.12604 1.2801  103 218.259 31506.30 2738.67
{n-Octane (1) + n-decane (2)}
0.0616 0.15324 1.2067  103 186.89 29050.16 2641.40
0.2801 0.15409 1.2093  103 195.255 30072.87 2719.15
0.5314 0.14382 1.2276  103 178.417 26904.08 2480.30
0.7736 0.1447 1.2323  103 194.047 29018.74 2629.55
0.9623 0.14185 1.2406  103 202.381 30103.08 2689.44

The excess molar volume behaviour for linear alkane mixtures pressure increases at fixed composition and temperature. The ap
tends to be negative over the whole range of composition for and jT for the {n-octane (1) + n-decane (2)} system are not pre-
almost all the cases at atmospheric pressure; therefore, the high- sented because they exhibit the same behaviour. However, the
pressure density results for both mixtures were compared with intervals are more reduced as ap varies from (0.8 to 1.3) 103 K1
literature data [3,5,8] at atmospheric pressure for the reported and jT varies from (0.8 to 2.2) 103 MPa1 due to the similarity
temperatures of (293.15 and 298.15) K. This was achieved by cor- of the molecules.
relating the experimental densities with equation (2); then, the
resulting parameters reported in table 14 were used to extrapolate
these data at atmospheric pressure. Finally, the extrapolated den- 4. Conclusions
sity data agree with those from references [3,5,8] with deviations
within 0.12%. The same high-pressure behaviour for the excess A static–synthetic cell coupled to a DMA–HPM densimeter from
molar volume was observed at atmospheric pressure for the data Anton Paar was used with a data acquisition system for density
reported by Cooper and Asfour [3]; the VE values calculated from measurements. Values of density for n-heptane and n-decane were
experimental densities exhibit positive behaviour. However, as found to be in agreement and within the deviation reported for the
for our VE values, they can be attributed to the low values which proposed equations and experimental data from the literature over
tend to zero using the corresponding uncertainties. the range studied from which it is considered that the apparatus is
The isobaric thermal expansivity ap and the isothermal com- able to measure densities with good precision. Ideal behaviour can
pressibility jT were calculated from the density function: be assumed for the two binary (n-heptane + n-decane) and (n-octa-
  ne + n-decane) systems according to the following statements: the
1 @ qm excess molar volume values are quite low, near to zero as the num-
ap ¼  ; ð4Þ
qm @T p ber of carbon atoms for both components are closer, exhibit nega-
tive values at about the intermediate compositions. The reported
 
1 @ qm u(VE) at the lowest and highest compositions with respect to the
jT ¼ : ð5Þ
more volatile component can approximate the VE values from po-
qm @p T
sitive to negative values.
The derivatives were solved using the five-parameter equation [28].
The resulting equations for ap and jT are
" # Acknowledgments
c4 =T 2 þ c5 =ð3T 4=3 Þ
ap ¼  ; ð6Þ
c3  ðc4 =T þ c5 =T 1=3 Þ þ p The authors thank the financial support of this research pro-
vided by Mexican Institutions: CONACyT and Instituto Politécnico
1 c2 Nacional.
jT ¼ 1=3
 : ð7Þ
c3  ðc4 =T þ c5 =T Þþp c1 þ c2 p
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