J. Chem. Thermodynamics 39 (2007) 254260 www.elsevier.

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Compressed liquid densities of 1-butanol and 2-butanol at temperatures from 313 K to 363 K and pressures up to 25 MPa
Abel Zuniga-Moreno, Luis A. Galicia-Luna *, Luis E. Camacho-Camacho
Laboratorio de Termodinamica, ESIQIE, Instituto Politecnico Nacional, Edif. Z, Secc. 6, 1ER Piso, UPALM, C.P. 07738, Mexico, D.F., Mexico Received 4 April 2006; received in revised form 4 July 2006; accepted 11 July 2006 Available online 4 August 2006

Abstract (p, q, T) properties were determined in liquid phase for 1-butanol and 2-butanol at temperatures from 313 K to 363 K and pressures up to 25 MPa using a vibrating tube densimeter. The uncertainty is estimated to be lower than 0.2 kg m3 for the experimental densities. Nitrogen and water were used as reference uids for the calibration of the vibrating tube densimeter. Experimental densities of 1-butanol and 2-butanol were correlated with a short empirical equation and the 11-parameter BenedictWebbRubinStarling equation of state (BWRS EoS) using a least square optimization. Statistical values to evaluate the dierent correlations were reported. Published densities of 1-butanol and 2-butanol are compared with values calculated with the BWRS EoS using the parameters obtained in this work. The experimental data determined here are also compared with available correlations for 1-butanol and 2-butanol. 2006 Elsevier Ltd. All rights reserved.
Keywords: 1-Butanol; 2-Butanol; BWRS EoS; Correlation; Density

1. Introduction Supercritical uid extraction represents an alternative in the recuperation of valuable products from natural resources [1]. A critical parameter in the development of this technology is the knowledge of (p, q, T) properties and phase equilibria of mixtures involving (CO2 + alkanol), as well as of pure compounds at high pressures. Supercritical uids containing CO2 and alkanol are interesting from both theoretical and practical point of view. For instance, CO2 is not capable to extract polar substances of high molecular weight, therefore the use of cosolvents have been proposed to enhance the solubility power of CO2 [1]. Our research is focused on a systematic study to obtain experimental VLE and (p, q, T) data of the (CO2 + alkanol) [29] mixtures for the knowledge, development and application of techniques directed towards supercritical extracCorresponding author. Tel.: +52 5729 6000x55133; fax: +52 5586 2728. E-mail address: lgalicial@ipn.mx (L.A. Galicia-Luna). 0021-9614/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.jct.2006.07.009
*

tion processes. The main objective is to perform systematic studies of phase equilibria of binary mixtures containing CO2 and alkanol and (p, q, T) measurements for these mixtures and pure alkanol (from ethanol to decanol) in order to select the best supercritical operating conditions required for industrial applications such as extraction of capsaicin from the chili Poblano of Mexico (Capsicum annum). On the other hand, the test and development of equations of state to calculate densities at high pressure is of importance in the chemical industry. In this work, compressed liquid densities for 1-butanol and 2-butanol from 313 K to 363 K and from 1 MPa to 25 MPa are reported herein. The experimental densities are correlated using two dierent equations: a 6-parameter equation [10] and the 11-parameter BenedictWebb RubinStarling equation of state (BWRS EoS) [11]. The consistency of the measurements has been checked by comparing experimental published data with density values calculated through the BRWS EoS with parameters tted on experimental data reported in this work. Our experimental data for 1-butanol are also compared to densities calculated with the correlations proposed by Cibulka and

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Zikova [12] and by Ihmels and Gmehling [13]. Those obtained for 2-butanol are compared to those calculated by the correlation proposed by Cibulka et al. [14]. 2. Experimental 2.1. Materials 1-Butanol (C4H10O, M = 74.123 g mol1, CAS-RN 7136-3) is from Aldrich with a stated purity >99.8 mol%. 2-butanol (C4H10O, M = 74.123 g mol1, CAS-RN 78-922) is from Aldrich with a stated purity of >99.5 mol%. Both alcohols were stored over a 3 A molecular sieve to avoid any moisture and were used without any further purication except with careful degassing. The purity of the liquids samples was tested using a gas chromatograph (HP 5890 Series II) tted with a Flame Ionization Detector (FID) and a packed column. The veried guaranteed purities in both cases are >99.5 mol%. Water is from Aldrich (HPLC grade, >99.95 mol%) and nitrogen is from Infra-Mexico (Chromatographic grade, 99.995 vol%). 2.2. Apparatus and procedure A detailed description of the apparatus was already given by Zuniga-Moreno and Galicia-Luna [79]. The measuring cell is composed of a vibrating tube (Hastelloy C-276 U-tube) with approximately 1 cm3 of internal volume. Temperatures are measured using Pt100 platinum probes (Specitec, France). Pressures are measured by means of a pressure transducer (Sedeme 250, France). The density values are obtained from the periods of oscillation of the vibrating tube. Vibrating tube was calibrated using water and nitrogen as reference uids [710]. The density of the uid, inside the U-tube, qF is giving by qF p; T qH2 O p; T   1 p; T s2 p; T s2 2 O p; T ; F H A 1 where qF(p, T), s2 p; T are the density and vibration periF od, respectively, of 1-butanol or 2-butanol and 1/A (p, T) is determined by qH O p; T qN2 p; T 1 p; T 2 2 : sH2 O p; T s2 2 p; T A N 2

In this work, estimated uncertainties are 0.03 K for temperatures, 0.008 MPa for pressures and 0.2 kg m3 for liquid densities at a 95% condence level. In the cell-loading step, the liquid (water, 1-butanol, or 2-butanol) is rst degassed and then distilled under vacuum and vigorous stirring into the evacuated feed cell. The temperature of this cell is regulated by means of an air bath with a thermal stability of 0.05 K. Measurements are made at constant temperature and the pressure measurements start at 1 MPa and it is increased approximately every 1 MPa up to reach 25 MPa. Four measurements for the same point are taken once the pressure and period signals are kept constant. Densities of dierent liquids have already been published (e.g. ethanol [7], 1-propanol [8], 2-propanol [8], thiophene [10], N,N-dimethylformamide [18], and decane [19]). Comparisons of experimental data with the literature data demonstrated the high accuracy and suitability of this measurement system. 3. Results and discussion Compressed liquid densities of 1-butanol and 2-butanol were determined at six temperatures from 313 K to 363 K and pressures up to 25 MPa and they are reported in tables 1 and 2. Densities of 1-butanol cover the density range between 753 kg m3 and 813 kg m3, while densities of 2-butanol covers the density range between 740 kg m3 and 809 kg m3. For each component the measured densities were correlated with two dierent models. A 6-parameter volume explicit equation was used and is represented as follows [10]: v d 1 d 2p ; d 3 d 4 T d 5 T 1=2 d 6 p 3

where v is the specic volume and di are adjustable parameters. This equation has been previously used to correlate densities of thiophene [10]. The 11-parameter BWRS EoS [11] is dened next p RT B0 RT A0 C 0 =T 2 D0 =T 3 E0 =T 4 Vm V2 m bRT a d=T aa d=T V3 V6 m m c1 u=V 2 expu=V 2 m ; V 3 T2 m 4

The reference density values for the nitrogen and water were obtained using the equations proposed by Wagner et al. [15,16]. The experimental procedure used here is that already described by Galicia-Luna et al. [17] and Zuniga-Moreno and Galicia-Luna [79]. The experimental procedure consists of four steps: 1 sensor calibration, 2 cell-loading, 3 setting up of the experimental conditions, and 4 measurements at equilibrium. A detailed calibration procedure of the platinum temperature probes and of the pressure transducer is given elsewhere by Galicia-Luna et al. [3,7].

where Vm is the molar volume. We have used the MarquardtLevenberg least squares optimization using the following objective function, S: X 2 S qi;exp qi;cal =qi;exp ; 5
i

to correlate the parameters of the dierent models. In order to evaluate the correlations, absolute average deviation (AAD), mean deviation (bias), standard deviation (SDV)

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TABLE 1 Experimental densities of 1-butanol at six temperatures 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 = 313.10 K 1.013 794.97 2.008 795.76 3.007 796.55 3.990 797.33 5.000 798.11 6.014 798.90 7.006 799.69 8.016 800.47 9.008 801.23 9.996 801.97 11.012 802.72 12.008 803.48 13.036 804.23 14.009 804.93 15.034 805.67 16.014 806.36 17.013 807.07 18.011 807.76 19.027 808.46 20.015 809.14 21.034 809.84 22.060 810.53 23.039 811.19 24.049 811.90 25.048 812.56

T = 323.08 K 1.040 787.23 2.043 788.06 3.005 788.88 4.009 789.70 5.014 790.53 6.024 791.38 7.062 792.21 8.033 792.99 9.025 793.79 10.008 794.58 11.020 795.36 12.027 796.15 13.044 796.95 14.035 797.69 15.055 798.46 16.063 799.21 17.039 799.93 18.057 800.67 18.995 801.37 20.045 802.11 21.090 802.85 22.039 803.52 23.078 804.27 24.010 804.94 25.055 805.68

T = 332.95 K 1.095 779.28 2.064 780.15 3.035 781.02 4.039 781.89 5.007 782.76 6.035 783.65 7.048 784.53 8.021 785.37 9.035 786.23 10.030 787.06 11.057 787.90 12.026 788.71 13.041 789.54 14.034 790.33 15.074 791.16 16.022 791.89 16.957 792.61 18.103 793.49 19.053 794.22 20.044 794.97 21.090 795.75 21.974 796.40 22.960 797.13 24.014 797.92 25.045 798.67

T = 342.89 K 1.021 771.26 2.060 772.26 3.051 773.20 4.044 774.13 5.014 775.03 6.024 775.96 7.050 776.88 8.037 777.76 9.052 778.65 10.057 779.53 11.053 780.38 12.027 781.22 13.077 782.09 14.026 782.86 15.080 783.73 16.028 784.48 17.031 785.27 18.020 786.04 19.009 786.80 20.030 787.58 21.066 788.35 21.978 789.03 23.061 789.83 24.031 790.55 25.045 791.30

T = 352.76 K 1.033 762.72 2.075 763.80 3.038 764.75 4.004 765.74 5.017 766.75 6.042 767.75 7.041 768.72 8.024 769.64 9.042 770.61 10.044 771.56 11.026 772.44 12.073 773.40 13.002 774.25 14.050 775.17 15.000 776.03 15.999 776.89 17.008 777.76 18.066 778.65 19.002 779.43 20.014 780.28 21.043 781.12 22.024 781.94 23.025 782.75 24.015 783.56 25.100 784.44

T = 362.68 K 1.031 753.17 2.065 754.33 3.038 755.40 4.026 756.45 5.050 757.54 6.018 758.55 6.995 759.56 8.100 760.70 9.002 761.62 10.021 762.62 10.995 763.58 12.059 764.62 13.056 765.56 14.029 766.47 15.024 767.42 16.010 768.33 17.020 769.25 18.041 770.16 19.031 771.05 20.045 771.93 21.016 772.76 22.022 773.64

TABLE 2 Experimental densities of 2-butanol at six temperatures 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 = 313.14 K 1.029 789.61 2.044 790.47 3.044 791.33 4.020 792.13 5.025 792.97 6.034 793.81 7.015 794.62 8.047 795.46 9.042 796.28 10.036 797.07 11.056 797.88 12.015 798.62 12.998 799.38 14.031 800.18 15.062 800.96 16.045 801.69 17.029 802.41 18.032 803.15 19.014 803.87 20.007 804.59 21.048 805.31 22.005 806.01 23.044 806.75 24.040 807.45 25.011 808.16

T = 323.12 K 1.024 780.71 2.019 781.62 3.028 782.53 4.054 783.45 5.025 784.31 6.046 785.21 7.009 786.05 8.016 786.93 9.036 787.81 10.038 788.67 11.085 789.54 12.007 790.30 13.058 791.16 14.013 791.95 15.014 792.76 16.058 793.57 17.014 794.33 18.066 795.16 19.017 795.87 20.012 796.64 21.035 797.41 22.018 798.15 23.008 798.89 24.063 799.69 25.023 800.41

T = 333.03 K 1.039 771.36 2.067 772.38 3.015 773.31 4.021 774.28 5.051 775.27 6.077 776.24 7.027 777.14 8.030 778.08 9.062 779.01 10.008 779.89 11.025 780.81 12.015 781.69 13.018 782.57 14.014 783.42 15.028 784.30 16.021 785.13 16.999 785.94 18.050 786.80 19.020 787.60 20.010 788.39 21.025 789.20 22.010 789.98 23.020 790.79 24.018 791.59 25.029 792.38

T = 342.96 K 1.035 761.81 2.085 762.95 3.051 763.94 4.055 764.99 5.022 765.98 6.004 766.98 7.054 768.04 8.030 769.00 9.030 769.98 10.053 770.95 11.019 771.86 12.025 772.81 13.011 773.71 14.015 774.61 15.006 775.48 16.036 776.39 17.036 777.26 18.028 778.10 19.010 778.91 20.038 779.76 21.011 780.56 22.029 781.38 23.030 782.18 24.002 782.96 25.033 783.79

T = 352.86 K 1.041 751.57 2.041 752.74 3.066 753.92 4.033 755.01 5.062 756.18 6.051 757.26 7.059 758.35 8.019 759.39 9.040 760.46 10.062 761.53 11.019 762.52 12.023 763.54 13.025 764.55 14.025 765.53 15.018 766.50 16.019 767.48 17.041 768.42 18.025 769.37 19.020 770.27 20.020 771.19 21.023 772.11 22.008 772.97 23.013 773.88 24.029 774.79 25.009 775.65

T = 362.79 K 1.034 740.13 2.005 741.38 3.035 742.67 3.999 743.86 5.056 745.14 6.053 746.34 7.031 747.50 8.032 748.66 9.052 749.84 10.045 750.95 11.009 752.02 12.031 753.14 13.018 754.21 14.007 755.25 15.026 756.31 15.999 757.31 17.038 758.37 18.013 759.36 18.998 760.34 20.016 761.31 21.005 762.29 22.009 763.23 23.012 764.19 24.007 765.14 25.037 766.09

and the root mean square (RMS) were used as statistical values for the two equations ts [18,19]. The parameters and statistical values [18,19] for the different correlations are reported in table 3 for 1-butanol and

for 2-butanol. In gure 1 the relative deviation of experimental densities of 1-butanol with density values calculated with the 6-parameter equation are shown. The two models (6-parameter and BWRS EoS) were capable to represent

 A. Zuniga-Moreno et al. / J. Chem. Thermodynamics 39 (2007) 254260 TABLE 3 Temperature, pressure and density range, number of data points (n), and parameters for the two correlation models of 1-butanol and 2-butanol along with statistical values 1-Butanol Tmin/K Tmax/K pmin/MPa pmax/MPa qmin/(kg m3) qmax/(kg m3) n 6-parameters d1/(MPa m3 kg1) d2/(m3 kg1) d3/MPa d4/(MPa K1) d5/(MPa K1/2) d6 AAD/% bias/% SDV/% RMS/% BWRS B0/(cm3 mol1) A0/(bar cm6 mol2) C0/(bar K2 cm6 mol2) D0/(bar K3 cm6 mol2) E0/(bar K4 cm6 mol2) b/(cm6 mol2) a/(bar cm9 mol3) d/(bar K cm9 mol3) c/(bar K2 cm9 mol3) a/(cm9 mol3) u/(cm6 mol2) AAD/% bias/% SDV/% RMS/% 313.10 362.68 1.013 25.100 753.17 812.56 147 5.035 0.0313 1329.4 16.067 435.1 29.1 0.02 0.001 0.02 0.02 531.73 3.7620 107 5.6987 1010 1.1190 1014 5.0227 1015 2.7788 104 8.4708 107 1.0768 1010 1.1766 1014 1.3360 107 8.3004 103 0.02 0.0003 0.02 0.02 2-Butanol 313.14 362.79 1.024 25.037 740.31 808.16 150 73.338 0.5352 6222.6 330.597 9469.8 488.9 0.02 0.001 0.02 0.02 539.57 2.6277 107 4.5535 1010 2.4466 1014 9.5956 1016 7.8240 103 8.1680 107 1.4154 1010 1.6557 1014 1.4473 107 4.7543 103 0.02 0.0002 0.02 0.02

257

the experimental measurements within the experimental uncertainty. Similar results were obtained for 2-butanol and this is graphically described in gure 2 for the case of the BWRS EoS. The short explicit volume equation allows rapid calculations in the range of temperature and pressure measured. The dierent available density data sets published in the literature for 1-butanol and 2-butanol are listed in table 4. 1-butanol has been more studied than 2-butanol. The experimental densities reported here for 1-butanol and 2-butanol complement the data sets reported in the literature, and the consistency of the experimental densities was done by comparing our experimental data (or the correlations obtained) with density data and correlations reported in the literature. Cibulka and Zikova [12] and Ihmels and Gmehling [13] reported two correlations using Tait-type equations. The correlation of Ihmels and Gmehling [13] was based only on their experimental density results, meanwhile the correlation proposed by Cibulka and Zikova was based in data published for dierent authors before 1993 [12]. Density values at the same conditions reported herein were calculated with the two mentioned equations. The relative deviation of experimental data from this work with calculated values with both correlations are shown in gure 3. Excellent agreement was found with the correlation proposed by Ihmels and Gmehling (TRIDEN) [13]. The maximum relative deviations are +0.08% and 0.06% as can be seen in gure 3. The deviations for the data reported in [13] with those obtained from the TRIDEN model, for the same range of temperature and pressure employed here, have maximum deviations of +0.07% and 0.02%. Results are similar for both cases, this point out the self-consistence between both data sets. For the comparison with the correlation from [12], the deviations are all positives (maximum

0.05 0.04 0.03 0.02

0.06 0.05 0.04 0.03

10 (1-cal)/1

0.01 0.00 -0.01 -0.02 -0.03 -0.04 -0.05 0 5 10 15 20 25

10 (1-cal)/1
2

0.02 0.01 0.00 -0.01 -0.02 -0.03 -0.04 -0.05 -0.06 0 5 10 15 20 25

p /MPa

p /MPa

FIGURE 1. Relative deviations of experimental densities for 1-butanol from this work (q1) and values calculated (qcal) with the 6-parameter equation using the adjusted parameters reported in table 3, at the following temperatures: s, 313.10 K; ,, 323.08 K; h, 332.95 K; }, 342.89 K; n, 352.76 K; and q, 362.68 K.

FIGURE 2. Relative deviations of experimental densities for 2-butanol from this work (q1) and values calculated (qcal) with the BWRS EoS using the adjusted parameters reported in table 3, at the following temperatures: s, 313.14 K; ,, 323.12 K; h, 333.03 K; }, 342.96 K; n, 352.86 K; and q, 362.79 K.

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TABLE 4 Characteristics of density data sets reported in the literature for 1-butanol and 2-butanol at high pressure Reference Bridgman [20] Bridgman [21] Goluveb and Bagina [22] Kubota et al. [23] Sahli et al. [24] Vasilkovskaya et al. [25] Zolin et al. [26] Goluveb et al. [27] Albert et al. [28] Kubota et al. [29] Wong and Hayduk [30] Papaioannou et al. [31] Shakhverdiev et al. [32] Ulbig et al. [33] Ihmels and Gmehling [13] Sahli et al. [24] Akhmedov et al. [34] Kubota et al. [29] Uosaki et al. [35]
*

n 30 5 171 90 14 92 15 103 18 48 18 10 40 9 336 14 71 48 4

Tmin/K 273.15 298.15 282.75 298.15 293.15 297.31 194.61 200.00 298.14 283.15 298.2 298.15 448.15 278.15 273.15 293.15 297.20 283.15 298.15

Tmax/K 1-Butanol 368.15 348.15 553.85 333.15 298.15 558.47 236.36 560.00 399.81 348.15 348.20 298.15 548.15 323.15 473.00 2-Butanol 298.15 473.70 348.15 298.15

pmin/MPa 49.0 980.6 0.2 1.0 1.0 1.0 1.0 1.0 0.2 15.5 0.6 0.1 0.5 20.0 0.29 1.0 0.1 15.4 50.0

pmax/MPa 1176.8 1863.2 50.6 150.0 7.0 49.1 49.1 50.0 20.5 206.1 6.9 33.9 58.6 60.0 40.0 7.0 49.0 206.5 200.0

Compound purity/% * * * 99.90 * 99.84 * 99.84 * >99.90 * * * >99.00 >99.80 99.50 99.40 >99.90 *

Not reported.

0.12 0.10 0.08 0.06

2 10 (1-cal)/1

0.04 0.02 0.00 -0.02 -0.04 -0.06 -0.08 -0.10 -0.12 0 5 10 15 20 25

and pressure range measured here were considered. The relative deviations for the dierent sets of data considered are plotted in gure 4. The maximum relative deviations are 0.2% as can be seen in gure 4 where dashed lines limited this range of deviations, only some points at 348.2 K reported by Wong and Hayduk [30] did not follow this trend being the deviations higher compared to the remaining data, these behavior was also found with the correlation of Ihmels and Gmehling [13]. The best agreement was observed with the reported by Kubota et al. [29] and

p /MPa

value: +0.1%); however, to evaluate this last comparison, the RMSD, RMSDr and bias as dened in [12] were calculated for our set of data, and the results are 0.038 kg m3, 0.005%, and 0.003 kg m3, respectively. These values are lower than those reported for individual sets of data used in the correlation [12]. This reects the good quality of our results. Additionally to these comparisons, the BWRS EoS with the parameters obtained here for 1-butanol was used to calculate densities at the same temperature and pressure of the data reported in the literature, however, only those data reported in the same range of temperature

10 (1-cal)/1
2

FIGURE 3. Relative deviations of experimental densities for 1-butanol from this work (q1) and values calculated (qcal) from the correlations reported by Cibulka and Zikova [12] and Ihmels and Gmehling [13], at the following temperatures: s, 313.10 K; ,, 323.08 K; h, 332.95 K; }, 342.89 K; n, 352.76 K; and q, 362.68 K. Open and closed symbols are for the correlations from [12 and 13], respectively.

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 -0.6 -0.7 -0.8 0 5 10 15 20 25

p /MPa

FIGURE 4. Comparison of the experimental densities for 1-butanol reported by dierent authors (q1) with the values calculated with the BWRS EoS (qcal) tted to data reported in this work; s, Goluveb and Bagina [22]; ,, Vasilkovskaya et al. [25]; h, Goluveb et al. [27]; }, Albert et al. [28]; n, Kubota et al. [29]; q, Wong and Hayduk [30]; d, Ulbig et al. [33]; , Ihmels and Gmehling [13].

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by Ihmels and Gmehling [13] since the deviations with these sets of data were represented with the uncertainty announced for the BWRS EoS. Most of the data of Golubev and Bagina [22] were in good agreement only a point at 20 MPa diers for the trend founded for the relative deviations for this set of data. The relative deviations with the data reported Albert et al. [28] were according to the uncertainty of 0.1% for the density measurements reported by the authors [28]. The systematic deviations with the data reported by Vasilkovskaya et al. [25] can be due to the lower purity of the 1-butanol used (99.84%). In gure 5, deviations of experimental densities reported in this work with the values calculated with the correlation reported by Cibulka et al. [14] for 2-butanol are plotted. The maximum deviations are 0.12%. As for the case of 1-butanol, the RMSD, RMSDr and bias as dened in [14] were calculated for our set of data, and the results are 0.38 kg m3, 0.05%, and 0.04 kg m3, respectively. These results are similar to those obtained for the individual sets of data used in the correlation [14]. This demonstrates good agreement between our experimental data with the correlation from [14]. The BWRS EoS with the parameters for 2-butanol obtained in this work was used to calculate densities at the temperature and pressure conditions reported by Kubota et al. [29] and by Akhmedov et al. [34] (data no used by Cibulka et al. [14] in their correlation), considering only data reported in the same range of temperature and pressure measured in this work. The relative deviations of calculated densities and the literature data [29,34] are shown in gure 6. Good agreement was observed with the data reported by Kubota et al. [29] being the relative deviations lower than 0.2%, however, the deviations are higher with the data reported by Akhmedov et al. [34] and these increased as the temperature increased, as it is depicted in gure 6. The temperatures in this study were selected taking into account the intended industrial applications of CO2 and
0.12 0.10 0.08 0.06

1.4 1.2 1.0

2 10 (1-cal)/1

0.8 0.6 0.4 0.2 0.0 4 6 8 10 12 14 16 18 20 22

p /MPa

FIGURE 6. Relative deviations of experimental densities reported in the literature (q1) and values calculated (qcal) with the BWRS EoS using the adjusted parameters reported in table 3 for 2-butanol; h, Kubota et al. [29]; s, Akhmedov et al., at 310.5 K [34]; and ,, Akhmedov et al., at 350.5 K [34].

binary mixtures containing (CO2 + alkanol) as a supercritical solvent for extracting components from natural products. 4. Conclusions Experimental determinations of densities were carried out at temperatures from 313 K to 363 K and pressures up to 25 MPa for 1-butanol and 2-butanol using a vibrating tube densimeter. The experimental measurements complement the data sets reported in the literature, especially for 2-butanol. The reported data are consistent with correlations published in the literature for 1-butanol and 2-butanol. A short empirical explicit volume equation was used to correlate the experimental densities to allow rapid calculations for the range of temperature and pressure measured here. Acknowledgments We thank CONACYT and IPN for their nancial support. References
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10 (1-cal)/1
2

0.04 0.02 0.00 -0.02 -0.04 -0.06 -0.08 -0.10 -0.12 0 5 10 15 20 25

p /MPa

FIGURE 5. Relative deviations of experimental densities from this work (q1) and values calculated (qcal) from the correlations reported by Cibulka et al. [14] for 2-butanol, at the following temperatures: s, 313.14 K; ,, 323.12 K; h, 333.03 K; }, 342.96 K; n, 352.86 K; and q, 362.79 K.

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JCT 06-84