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J. Chem. Thermodynamics 39 (2007) 254–260 Luis

J. Chem. Thermodynamics 39 (2007) 254–260 Luis

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J. Chem. Thermodynamics 39 (2007) 254–260 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 Æ mÀ3 for the experimental densities. Nitrogen and water were used as reference fluids 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 Benedict–Webb–Rubin–Starling equation of state (BWRS EoS) using a least square optimization. Statistical values to evaluate the different 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. Ó 2006 Elsevier Ltd. All rights reserved.
Keywords: 1-Butanol; 2-Butanol; BWRS EoS; Correlation; Density

1. Introduction Supercritical fluid 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 fluids 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) [2–9] 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 Ó 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 different equations: a 6-parameter equation [10] and the 11-parameter Benedict–Webb– Rubin–Starling 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 fitted 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

Densities of different liquids have already been published (e. T Þ þ   1 ðp. and 4 – measurements at equilibrium.´˜ A. The purity of the liquids samples was tested using a gas chromatograph (HP 5890 Series II) fitted with a Flame Ionization Detector (FID) and a packed column. qF is giving by qF ðp. 2 – cell-loading. inside the U-tube. Water is from Aldrich (HPLC grade. A detailed calibration procedure of the platinum temperature probes and of the pressure transducer is given elsewhere by Galicia-Luna et al. T Þ 1 ðp. S: X Ã2 S¼ ðqi. France). Four measurements for the same point are taken once the pressure and period signals are kept constant. [17] and Zuniga-Moreno and Galicia-Luna [7–9].7]. 99. F H A ð1Þ where qF(p.95 mol%) and nitrogen is from Infra-Mexico (Chromatographic grade. of 1-butanol or 2-butanol and 1/A (p. Thermodynamics 39 (2007) 254–260 255 Zikova [12] and by Ihmels and Gmehling [13]. s2 ðp. d 3 À d 4 T þ d 5 T 1=2 þ d 6 p ð3Þ where v is the specific volume and di are adjustable parameters. T) is determined by qH O ðp. The density values are obtained from the periods of oscillation of the vibrating tube. 2-butanol (C4H10O.cal Þ=qi. T Þ s2 ðp. The density of the fluid.2. 2-propanol [8]. ð5Þ i to correlate the parameters of the different models. A 6-parameter volume explicit equation was used and is represented as follows [10]: v¼ d 1 þ d 2p . In the cell-loading step. T Þ are the density and vibration periF od. or 2-butanol) is first degassed and then distilled under vacuum and vigorous stirring into the evacuated feed cell.995 vol%). T Þ À s2 2 ðp. ethanol [7]. We have used the Marquardt–Levenberg least squares optimization using the following objective function. In order to evaluate the correlations. [14]. T Þ ¼ 2 2 : sH2 O ðp.5 mol%. Both ˚ alcohols were stored over a 3 A molecular sieve to avoid any moisture and were used without any further purification except with careful degassing.123 g Æ molÀ1. 1-propanol [8]. Materials 1-Butanol (C4H10O.N-dimethylformamide [18]. Experimental 2. CAS-RN 78-922) is from Aldrich with a stated purity of >99. 3 – setting up of the experimental conditions. The verified guaranteed purities in both cases are >99. and decane [19]). The temperature of this cell is regulated by means of an air bath with a thermal stability of 0. thiophene [10]. T Þ ¼ qH2 O ðp. Zuniga-Moreno et al. Pressures are measured by means of a pressure transducer (Sedeme 250. standard deviation (SDV) . 2. [3. T Þ À s2 2 O ðp. The experimental procedure consists of four steps: 1 – sensor calibration. 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. M = 74. mean deviation (bias). T). Those obtained for 2-butanol are compared to those calculated by the correlation proposed by Cibulka et al.16]. For each component the measured densities were correlated with two different models. >99. Apparatus and procedure A detailed description of the apparatus was already ´˜ given by Zuniga-Moreno and Galicia-Luna [7–9].5 mol%. [15.05 K.g.exp . Chem. the liquid (water. Comparisons of experimental data with the literature data demonstrated the high accuracy and suitability of this measurement system. 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. Vibrating tube was calibrated using water and nitrogen as reference fluids [7–10]. 3.008 MPa for pressures and ±0. / J.123 g Æ molÀ1.exp À qi. T Þ A N ð2Þ In this work. T Þ À qN2 ðp. The measuring cell is composed of a vibrating tube (Hastelloy C-276 U-tube) with approximately 1 cm3 of internal volume. respectively. absolute average deviation (AAD). France). Densities of 1-butanol cover the density range between 753 kg Æ mÀ3 and 813 kg Æ mÀ3. CAS-RN 7136-3) is from Aldrich with a stated purity >99. V 3 T2 m ð4Þ The reference density values for the nitrogen and water were obtained using the equations proposed by Wagner et al. N.8 mol%. The experimental procedure used here is that already ´˜ described by Galicia-Luna et al. M = 74. Temperatures are measured using Pt100 platinum probes (Specitec. 2. estimated uncertainties are ±0. ±0.03 K for temperatures. T Þ . This equation has been previously used to correlate densities of thiophene [10]. 1-butanol. where Vm is the molar volume.1. while densities of 2-butanol covers the density range between 740 kg Æ mÀ3 and 809 kg Æ mÀ3. The 11-parameter BWRS EoS [11] is defined next p¼ RT ðB0 RT À A0 À C 0 =T 2 þ D0 =T 3 À E0 =T 4 Þ þ þ Vm V2 m ðbRT À a À d=T Þ aða þ d=T Þ þ þ V3 V6 m m cð1 þ u=V 2 Þ expðÀu=V 2 Þ m .2 kg Æ mÀ3 for liquid densities at a 95% confidence level.

19].103 793.025 772.051 763.81 7.031 790.035 797.032 803.31 22.060 772.62 12.76 9.062 756.080 783.031 785.38 T = 342.62 8.16 14.025 764.62 3.047 795.94 23.009 786.035 786.004 765.042 770.66 9.41 18.33 5.28 10.94 4.008 779.05 8.018 782.04 19.063 799.005 806.14 21.974 796.026 772.041 768.002 782.44 12.67 16.053 794.38 14.045 801.42 18.027 781.026 756.000 776.045 791.61 10.025 780.064 780.05 20.014 780.011 780.018 766.036 777.61 18. The two models (6-parameter and BWRS EoS) were capable to represent .62 10.002 774.03 23.18 6.72 12.062 761.76 6.03 K 1.28 5.017 795.93 9.014 775.53 23.025 769.61 15.76 K 1.56 14.50 16.88 8.06 3.034 809.051 773.89 11.073 773.021 762.03 15.86 15.022 791.999 776.024 780.019 781.045 771.13 5.84 22.58 12.19 24.94 18.035 781.041 751.10 K 1.025 765.009 804.17 2.040 787.94 25.88 12.14 8.52 23.050 757.008 795.007 790.029 766.015 794.38 3.55 3.56 25.96 7.007 755.24 7.21 17.029 774.25 14.002 779.029 792.15 19.75 7.14 K 1.75 24.01 10.35 8.55 6.026 788.057 779.028 782.86 5.011 773.45 5.95 11.028 784.006 799.021 774.12 22. Zuniga-Moreno et al.066 778.038 764.53 11.69 15.013 791.027 777.50 8.036 787.12 K 1.020 771.018 754.033 792.025 789.039 803.012 764.052 778.020 786.085 762.015 783.028 784.56 8.53 8.20 4.60 20.31 4.999 757.016 772. Chem.061 789.86 12.07 11.33 15.031 747.055 798.37 9.58 11.035 783.016 761.18 24.37 18.89 24.71 13.995 801.067 772.17 15.007 765.010 768.009 775.11 6.024 791.044 794.015 773.08 K 1.46 20.023 800.017 766.58 21.72 8.42 16.55 25.76 18.56 11.88 24.035 797.33 18.09 14.050 786.80 20.87 20.020 792.06 11.54 13.040 807.48 16.14 6.93 15.026 782.037 766.11 21.019 759.79 10.97 11.020 769.99 9.02 4.052 749.97 2.043 781.01 5.38 7.013 759.89 17.36 2.040 760.044 774.060 810.96 25.012 796.042 796.051 775.030 769.75 4.035 761.68 K 1.69 8.039 799.044 791.26 2.15 3.10 19.56 T = 323.031 753.43 20.053 780.009 752.015 798.26 18.33 4.065 754.995 759.13 2.034 793.041 752. The parameters and statistical values [18.978 789.059 758.066 795.31 17.036 776.044 796.15 13.54 6.998 760.031 753.36 12.97 23.96 16.020 770.33 17.031 771.058 793.049 811.93 21.030 778.48 17.038 755.996 801.67 11.47 9.043 788.999 785.54 14.69 13.00 9.038 758.075 763.053 770.40 4.70 5.045 802.64 TABLE 2 Experimental densities of 2-butanol at six temperatures p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) T = 313.010 804.67 3.009 789.16 19.31 6.010 789.65 19.13 16.62 13.13 24.95 15.056 745.02 12.039 781.55 14.014 783.39 17.16 19.40 13.036 804.98 6.062 800.041 770.45 25.67 18.16 T = 323.01 23.74 3.76 21.76 19.014 797.029 802.97 21.39 9.034 740.79 24.19 21.022 765.013 794.012 802.64 9.27 6.990 797.005 788.57 17.007 782.044 790.90 25.014 794.027 796.033 755.041 789.65 7.30 16.23 23.23 14.34 7.048 812.048 784.034 805.045 750.029 781.21 8.066 753.21 14. Thermodynamics 39 (2007) 254–260 TABLE 1 Experimental densities of 1-butanol at six temperatures p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) p/MPa q/(kg Æ mÀ3) T = 313.006 775.056 765.03 6.59 25.020 795.056 797.050 775.009 763.066 788.033 783.025 792.70 9.028 778.85 22.46 9.019 762.062 792.95 11.000 798.89 K 1.015 809.53 6.09 and the root mean square (RMS) were used as statistical values for the two equations fits [18.995 763.008 798.39 21.08 9.010 778.25 15.81 13.56 22.100 760.98 7.031 800.46 16.059 764.86 K 1.48 13.38 12.33 3.80 3.62 10.074 791.98 23.27 18.034 790.998 799.077 782.23 2.024 769.35 21.75 6.47 15.090 802.74 5.95 3.002 761.84 10.89 5.16 16.024 767.91 20.27 20.79 K 1.057 787.036 797.013 807.053 746.018 791.054 783.30 T = 352.957 792.026 756.090 795.53 4.256 ´˜ A.008 801.014 792.029 789.005 762.57 2.69 25.037 777.050 776.045 798.30 13.29 22.007 804.31 21.960 797.59 21.53 11.45 5.18 15.93 18.31 15.14 13.024 775.022 773.018 798.038 788.69 17.008 794.49 19.035 742.057 800.88 4.014 790.41 T = 333.76 16.025 793.021 785.42 15.21 7.96 K 1.030 787.75 24.57 14.077 776.81 10.021 785.038 779.99 5.20 22.014 806.055 805.22 13.013 773.76 22.030 787.19] for the different correlations are reported in table 3 for 1-butanol and for 2-butanol.90 7.008 803.23 10.016 786.042 767.81 2.47 3.54 12.019 771.38 3.28 21.016 800.024 781.020 790.021 771.71 2.44 T = 362.19 24.14 25.07 18.025 784.015 774.41 22.80 19.025 782.53 15.89 16.26 3.40 22.085 789.051 757.033 762.83 24.058 791.999 743.019 767.26 7.046 785.095 779.055 764.030 782.062 779.078 804.37 20.87 20. In figure 1 the relative deviation of experimental densities of 1-butanol with density values calculated with the 6-parameter equation are shown.063 799.015 781.11 22.032 748.37 19.008 777.28 2.13 5.68 T = 332.010 788.044 771.81 12.04 8.007 796.008 772.98 10.020 787.64 21.75 21.22 20.018 758.039 811.048 805.36 17.72 2.030 769.38 23.67 T = 342.79 T = 352.014 803.039 771.79 25. / J.46 10.009 786.15 23.023 772.61 2.73 16.023 763.36 18.005 741.95 K 1.25 18.004 766.054 768.95 14.76 3.041 768.52 12.027 808.65 10.97 6.90 12.044 806.71 14.23 9.011 808.92 25.92 4.27 24.65 T = 362.100 784.48 17.014 798.34 20.011 807.

31 808.01 -0.08 K. meanwhile the correlation proposed by Cibulka and Zikova was based in data published for different authors before 1993 [12].4154 Æ 1010 À1. Zuniga-Moreno et al.03 -0.03 0.10 362.02 0.0768 Æ 1010 À1..02 0.1190 Æ 1014 À5. Similar results were obtained for 2-butanol and this is graphically described in figure 2 for the case of the BWRS EoS.024 25.17 812. 323.1 0.02%. . Cibulka and Zikova [12] and Ihmels and Gmehling [13] reported two correlations using Tait-type equations.04 -0.6277 Æ 107 4. h.05 0.0313 À1329.02 À0. The short explicit volume equation allows rapid calculations in the range of temperature and pressure measured.14 K. 342.1766 Æ 1014 1.68 K.76 K. FIGURE 2.14 362. number of data points (n).7620 Æ 107 5.02 0.02 257 the experimental measurements within the experimental uncertainty. and q.05 0. Thermodynamics 39 (2007) 254–260 TABLE 3 Temperature.89 K.4708 Æ 107 1. 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 3.00 -0. 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 Æ mÀ3) qmax/(kg Æ mÀ3) n 6-parameters d1/(MPa Æ m3 Æ kgÀ1) d2/(m3 Æ kgÀ1) d3/MPa d4/(MPa Æ KÀ1) d5/(MPa Æ KÀ1/2) d6 AAD/% bias/% SDV/% RMS/% BWRS B0/(cm3 Æ molÀ1) A0/(bar Æ cm6 Æ molÀ2) C0/(bar Æ K2 Æ cm6 Æ molÀ2) D0/(bar Æ K3 Æ cm6 Æ molÀ2) E0/(bar Æ K4 Æ cm6 Æ molÀ2) b/(cm6 Æ molÀ2) a/(bar Æ cm9 Æ molÀ3) d/(bar Æ K Æ cm9 Æ molÀ3) c/(bar Æ K2 Æ cm9 Æ molÀ3) a/(cm9 Æ molÀ3) u/(cm6 Æ molÀ2) AAD/% bias/% SDV/% RMS/% 313.100 753.12 K.57 2. 362.338 À0.1680 Æ 107 1.7543 Æ 103 0. have maximum deviations of +0.06 0.04 0. Density values at the same conditions reported herein were calculated with the two mentioned equations. For the comparison with the correlation from [12].02 0.5352 À6222.79 1.79 K.04 0.10 K.3360 Æ 107 8.06% as can be seen in figure 3.01 0.02 0.02 0.0003 0. 352.96 K.03 K.6 À330.8 À488. h.067 À435. 333.02 539.7788 Æ 104 8. at the following temperatures: s.. 332. The relative deviation of experimental data from this work with calculated values with both correlations are shown in figure 3.´˜ A. and q.02 0. 313.4473 Æ 107 4.86 K.05 -0.02 0.08% and À0. pressure and density range. n.68 1. this point out the self-consistence between both data sets. The maximum relative deviations are +0. The correlation of Ihmels and Gmehling [13] was based only on their experimental density results.6557 Æ 1014 1.0227 Æ 1015 2.6987 Æ 1010 1.1 À29. }.0002 0.4 À16. 323.02 2-Butanol 313.95 K.035 À0.02 -0. The deviations for the data reported in [13] with those obtained from the TRIDEN model.01 -0. 313. 352. Excellent agreement was found with the correlation proposed by Ihmels and Gmehling (TRIDEN) [13]. }.9 0.06 0 5 10 15 20 25 2 p /MPa p /MPa FIGURE 1. / J. n. .73 3.001 0.00 -0.3004 Æ 103 0.02 -0.013 25.16 150 À73. for the same range of temperature and pressure employed here. 362.03 10 (ρ1-ρcal)/ρ1 0. Results are similar for both cases.8240 Æ 103 8. 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.037 740.5535 Æ 1010 À2. . The different available density data sets published in the literature for 1-butanol and 2-butanol are listed in table 4.4466 Æ 1014 À9.597 À9469. 1-butanol has been more studied than 2-butanol.03 -0.01 0. Chem. The experimental densities reported here for 1-butanol and 2-butanol complement the data sets reported in the literature. the deviations are all positives (maximum 0. 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 3.001 0. 342.05 0 5 10 15 20 25 10 (ρ1-ρcal)/ρ1 2 0.56 147 À5. at the following temperatures: s.02 0.04 -0.02 531.07% and À0.5956 Æ 1016 7.

6 -0.15 553. only those data reported in the same range of temperature 10 (ρ1-ρcal)/ρ1 2 FIGURE 3. Open and closed symbols are for the correlations from [12 and 13].0 pmax/MPa 1176. these behavior was also found with the correlation of Ihmels and Gmehling [13].. n.06 2 10 (ρ1-ρcal)/ρ1 0.1 15. h.2 K reported by Wong and Hayduk [30] did not follow this trend being the deviations higher compared to the remaining data. 0. Wong and Hayduk [30].2 298. }. [24] Vasilkovskaya et al.15 298.04 0. and the results are 0.6 0.5 0.15 548.5 206.20 283.95 K.2 0.2 1. 0. to evaluate this last comparison.15 278.15 297. [27]. d. Goluveb et al.15 473.15 297.68 K. respectively.15 Tmax/K 1-Butanol 368. only some points at 348.04 -0.00 2-Butanol 298.258 ´˜ A.1 49.36 560.2 15.81 348. s.0 49. Goluveb and Bagina [22].1 -0.50 99.0 1.75 298. [28].90 * Not reported.15 282. The best agreement was observed with the reported by Kubota et al.1 50. [25]. however.02 -0.1 6. [29].2 50.0 980.005%. Zuniga-Moreno et al.08 K.7 -0.61 200.2 -0. [29] Wong and Hayduk [30] Papaioannou et al. [24] Akhmedov et al.6 60. [33]. 362.0 -0.29 1.15 323. .6 0.10 -0. 323.0 7.9 58.10 K.0 0. [35] * n 30 5 171 90 14 92 15 103 18 48 18 10 40 9 336 14 71 48 4 Tmin/K 273.1%).08 -0. respectively.0 206. 332. [29] Uosaki et al. Albert et al.84 * 99. Additionally to these comparisons.4 -0. 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].20 298. Chem.0 40. [33] Ihmels and Gmehling [13] Sahli et al.15 473.5 200. [29] and p /MPa value: +0. 352. the RMSD.9 33.8 0. however. Thermodynamics 39 (2007) 254–260 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. This reflects the good quality of our results.15 298.2% as can be seen in figure 4 where dashed lines limited this range of deviations. .5 20.40 >99.15 293.12 0. at the following temperatures: s. [28] Kubota et al. RMSDr and bias as defined in [12] were calculated for our set of data.15 293. ·.12 0 5 10 15 20 25 and pressure range measured here were considered.47 236.90 * 99. [26] Goluveb et al.5 0.15 pmin/MPa 49. .6 150.15 298. The relative deviations for the different sets of data considered are plotted in figure 4. Comparison of the experimental densities for 1-butanol reported by different authors (q1) with the values calculated with the BWRS EoS (qcal) fitted to data reported in this work.00 -0.4 0.0 1.06 -0..5 -0.00 399. [25] Zolin et al.76 K. n. Ihmels and Gmehling [13].3 0.10 0. and 0.1 0.0 0.80 99.3 -0.70 348.8 1863.0 49.85 333.15 298. 342. Vasilkovskaya et al. [23] Sahli et al.15 558.1 0.00 298. h.0 0. [27] Albert et al. / J.7 0. [31] Shakhverdiev et al.15 448. [34] Kubota et al.0 20.003 kg Æ mÀ3. Kubota et al.15 348. Ulbig et al. The maximum relative deviations are ±0.8 0 5 10 15 20 25 p /MPa FIGURE 4. 0.84 * >99.15 348. 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.02 0.0 1.15 298. 313.08 0. These values are lower than those reported for individual sets of data used in the correlation [12]. q.15 273.14 283. }.31 194.4 50. and q.89 K.0 Compound purity/% * * * 99.00 >99.0 7.0 1.6 0. [32] Ulbig et al.90 * * * >99.038 kg Æ mÀ3.

[6] O. respectively. 10 (ρ1-ρcal)/ρ1 2 0. L. Akhmedov et al. [14] for 2-butanol.0 4 6 8 10 12 14 16 18 20 22 p /MPa FIGURE 6.12%. Fluid Phase Equilibr. Ortega-Rodrıguez. Thermodynamics 39 (2007) 254–260 259 by Ihmels and Gmehling [13] since the deviations with these sets of data were represented with the uncertainty announced for the BWRS EoS.06 1. [14] in their correlation). CRC Press.4 0. [2] J. and the results are 0. 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.2 0.A. [29] being the relative deviations lower than 0. 2000. These results are similar to those obtained for the individual sets of data used in the correlation [14]. Eng. Sandler. Chem. [34] and these increased as the temperature increased. s. ´ [3] L.8 0.10 0. at 310. at the following temperatures: s. and q.84%). Akhmedov et al. the deviations are higher with the data reported by Akhmedov et al. The temperatures in this study were selected taking into account the intended industrial applications of CO2 and 0. at 350. h. L.A.02 -0. 210 (2003) 215–227. 0.79 K. ELDATA: Int.. Richon. Boca Raton.L. Fluid Phase Equilibr.10 -0. S. 333.08 -0. This demonstrates good agreement between our experimental data with the correlation from [14]. 182 (2001) 145–156..5 K [34]. L. D.12 0 5 10 15 20 25 p /MPa FIGURE 5. 352. References [1] M.34] are shown in figure 6. and .6 0. Zuniga-Moreno et al.´˜ A. Silva-Oliver. however. Natural Extracts Using Supercritical Carbon Dioxide. 342. Good agreement was observed with the data reported by Kubota et al. [29]. The reported data are consistent with correlations published in the literature for 1-butanol and 2-butanol. J.I.A.38 kg Æ mÀ3. The relative deviations of calculated densities and the literature data [29. deviations of experimental densities reported in this work with the values calculated with the correlation reported by Cibulka et al. 323.08 0. Phys. Data 5 (1999) 157–164.G. Fluid Phase Equilibr. [29] and by Akhmedov et al. the RMSD. especially for 2-butanol.14 K.96 K. 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.5 K [34]. J. S.. Galicia-Luna. [14] for 2-butanol are plotted.12 0. . [25] can be due to the lower purity of the 1-butanol used (99. 200 (2002) 161–172. [4] G. Mukhopadhyay.06 -0.04 kg Æ mÀ3. 362.05%. 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.12 K.00 -0.2%. Chem. [28] were according to the uncertainty of ±0. The relative deviations with the data reported Albert et al. Sandler. 4. Mendoza de la Cruz. A. FL. Relative deviations of experimental densities from this work (q1) and values calculated (qcal) from the correlations reported by Cibulka et al.A. Chem. }. [5] G.4 1. Silva-Oliver. h.04 0. Data 45 (2000) 265–271. Electron. and 0. 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. Galicia-Luna.04 -0. The systematic deviations with the data reported by Vasilkovskaya et al. Acknowledgments We thank CONACYT and IPN for their financial support. The experimental measurements complement the data sets reported in the literature. considering only data reported in the same range of temperature and pressure measured in this work. Galicia-Luna. binary mixtures containing (CO2 + alkanol) as a supercritical solvent for extracting components from natural products. Most of the data of Golubev and Bagina [22] were in good agreement only a point at 20 MPa differs for the trend founded for the relative deviations for this set of data.02 0. The maximum deviations are ± 0.03 K. Elizalde-Solis. J. 313.I. As for the case of 1-butanol. Galicia-Luna. [34] (data no used by Cibulka et al.86 K. / J. .2 1. L. In figure 5.A. Kubota et al. Galicia-Luna.1% for the density measurements reported by the authors [28].0 2 10 (ρ1-ρcal)/ρ1 0. n.. Sampayo´ Hernandez. RMSDr and bias as defined in [14] were calculated for our set of data. as it is depicted in figure 6.

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