Article pubs.acs.org/jced
Vapor Pressures of 2‑Chloro-3,3,3-trifluoropropene (HCFO-1233xf) Wei Zhang, Zhi-qiang Yang, Jing Lu, and Jian Lu* Xi’an Modern Chemistry Research Institute, Xi’an, Shaanxi 710065, People’s Republic of China ABSTRACT: The vapor pressure of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) was measured in the temperature range from (263 to 373) K and at pressure between (43 and 1139) kPa. The experimental data including 99 points were collected, and were correlated by the Antoine equation. The absolute deviation and relative deviation were less than ± 0.5 kPa and ± 0.5 %, respectively. The results were also fitted by the Wagner equation.
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INTRODUCTION Hydrofluorocarbons (HFCs) are potent greenhouse gases. Their global warming potentials (GWP) are much larger than carbon dioxide. In response to the climate change issue, Kyoto protocol has established the phased out of HFCs in the near future, and the refrigerants that have a GWP over 150 level was banned from use in new automotive air conditioning systems in the European Union.1 Thus, lower GWP refrigerants are required to replace HFC-134a (1,1,1,2-tetrafluoroethane), the most used refrigerant with GWP of 1430. Currently, HFO1234yf (2,3,3,3-tetrafluoropropene) is recognized as a possible drop-in alternative for HFC-134a because of its substantially low GWP of 4 and zero ozone depletion potential.2 Until now, a large number of patents have reported several synthetic routes used HCFO-1233xf (2-chloro-3,3,3-trifluoropropene) as the important raw material or intermediate for manufacture of HFO-1234yf.3,4 For a fluid, the vapor pressure as a significant thermophysical parameter is required for design and operation of multicomponent systems. However, to our best knowledge, there are very few studies on the thermodynamic properties of HCFO1233xf in the published literature.5 No systematic data of vapor pressure are available for HCFO-1233xf. In this work, the saturated vapor pressures of HCFO-1233xf were measured in the temperature range from (263 to 373) K, corresponding to pressures from (43 to 1139) kPa. The present results were correlated by the Antoine equation and the Wagner equation.
The GC analysis confirmed that the purity of samples were above 99.9 % on a mass basis. Apparatus. The apparatus used in this work was similar to that used by Wang et al.6 The scheme of the experimental apparatus is shown in Figure 1. It includes a thermostatic bath and a sample cell with measurement system of temperature, pressure, and vacuum system. The temperature of thermostat bath could be varied from (233 to 423) K using methylsilicone oil as the bath fluid. The temperature instability was within 2 mK over a period of 1 h. The temperature measurement system includes platinumresistance thermometers (Yunnan Instrument, China; no. 4349) with an uncertainty of ± 2 mK, a data acquisition/ switch unit (Agilent, 34970A) with an uncertainty of less than 1 mK by calibration against the ITS-90 at the China National Institute of Metrology. The overall temperature uncertainty for the bath and the temperature measurement system was less than ± 10 mK. The temperature of the thermostatic bath is controlled by computer, which controls the electric power of the heaters based on an incremental digital PID algorithm. The measurement system of pressure includes a differential pressure transducer (Xian Instrument, China; 1151DP) used from (−10 to +10) kPa with a full scale uncertainty of ± 0.25 %, and an absolute pressure sensor (GE, PMP4051) used from (0 to 3.2) MPa with a full scale uncertainty of ± 0.04 %. The overall maximum experimental uncertainty in this measurement system of pressure is estimated to be less than 1.2 kPa. The sample cell with an approximate volume of 50 mL was used in this work. Before test, to remove any residue from last experiment the sample cell was thoroughly cleaned out with acetone. After the cell was filled with sample, the temperature of thermostat bath was heated to the experimental temperature. The temperature and the pressure of sample were measured when thermal equilibrium was established between the sample and the heat transfer fluid in the bath with the constant pressure.
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EXPERIMENTAL SECTION Materials. HCFO-1233xf was provided by Xi’an Modern Chemistry Research Institute. HFC-245fa (1,1,1,3,3-pentafluoropropane) was provided by Zhejiang Fluoro-Chemical Technology Research Institute. Before use the sample cell was loaded into liquid nitrogen and degassed to remove gaseous impurity in HFC-245fa or HCFO-1233xf. The purity of sample was determined by gas chromatography (Shimadzu GC-2010) equipped with a flame ionization detector and a capillary column (PLOT Al2O3 S, Agilent model 19091P-S33). © 2013 American Chemical Society
Received: April 26, 2013 Accepted: July 10, 2013 Published: July 22, 2013 2307
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Figure 1. Scheme of the apparatus. A, pressure sensors; B, digital multimeter; C, pressure bumper; CL, cooler; D, nitrogen bottle; DP, differential pressure detector; E, vacuum pump; F, pressure gauge; G, pressure balance controller; H, sample cell; HT, heater; J, thermostatic bath; K, auxiliary cooler; PC, computer; PT, platinum resistance thermometer; SP, standard platinum resistance thermometer; V1 to V9, valves.
Table 1. Experimental Vapor Pressures of HFC-245fa Compared with Pcal Calculated by the Wagner Equationa
a
T/K
P/kPa
Pcal/kPa
100(P − Pcal)/P
T/K
P/kPa
Pcal/kPa
100(P − Pcal)/P
260.32 272.13 281.15 293.31 305.49 313.62
28.52 50.91 75.62 122.98 192.78 254.28
28.65 50.72 75.53 123.46 192.92 254.10
−0.45 0.36 0.11 −0.39 −0.07 0.07
321.40 333.49 345.16 351.47 364.00 377.04
324.38 467.72 642.26 754.32 1028.15 1378.24
325.71 466.7 642.9 756.72 1027.17 1379.2
−0.41 0.22 −0.10 −0.32 0.09 −0.07
Standard uncertainties are u(T) = 0.03 K and u(P) = 1.2 kPa.
Table 2. Experimental Vapor Pressures of HCFO-1233xfa
a
T/K
P/kPa
T/K
P/kPa
T/K
P/kPa
T/K
P/kPa
263.25 264.27 265.23 266.27 267.22 267.16 268.20 269.08 270.04 270.94 270.95 271.90 273.85 274.80 275.39 277.03 277.96 278.77 278.99 279.80 280.56 281.62 282.80 283.65 284.51
43.43 45.20 47.13 48.88 50.69 51.02 52.65 55.20 57.24 59.24 59.34 61.45 66.42 68.69 70.68 75.24 77.86 80.20 81.33 83.72 85.87 89.39 93.36 95.62 98.59
285.10 286.15 287.18 288.59 289.24 290.31 292.20 294.48 296.12 297.41 298.46 299.53 300.22 301.38 303.03 304.22 305.36 306.37 307.38 308.45 309.44 311.14 312.65 313.32 314.65
100.84 103.78 107.59 113.20 115.72 120.08 128.29 138.49 146.32 152.85 158.20 164.03 167.73 174.15 183.59 191.32 198.32 205.25 212.61 219.76 226.88 239.23 250.71 255.58 265.41
315.41 316.41 317.54 318.54 319.54 320.20 321.51 322.39 322.28 323.27 324.40 325.16 326.17 327.54 328.16 329.38 330.27 331.36 332.28 333.37 333.10 334.34 335.18 336.20 337.33
271.67 279.99 288.86 296.49 305.35 312.84 323.90 331.79 330.90 340.55 351.13 359.71 370.10 383.61 390.36 402.72 412.59 424.58 434.81 447.55 444.59 462.26 468.47 480.83 494.73
338.30 339.24 340.43 341.35 342.53 342.25 344.38 345.78 346.77 347.88 348.77 349.98 350.86 352.84 354.89 356.87 358.89 360.78 362.63 364.64 366.88 368.89 370.88 372.90
506.41 518.13 533.53 545.17 561.23 558.82 589.61 613.34 629.58 646.33 660.14 679.92 695.77 728.61 762.84 799.73 838.22 874.39 916.57 957.20 1003.68 1047.81 1093.00 1138.94
Standard uncertainties are u(T) = 0.03 K and u(P) = 1.2 kPa.
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RESULTS AND DISCUSSION Now, only several points involved with the thermophysical properties of HCFO-1233xf are reported in the patent.5 Therefore, a similar compound HFC-245fa was first employed to examine the reliability of our experimental setup. Twelve points of vapor pressure were obtained for HFC-245fa at temperature from (260 to 377) K. Table 1 shows the measured data of vapor pressure for HFC-245fa with the data calculated by the Wagner equation.6 The relative deviations between the experimental and calculated data were within ± 0.5 %. Hence, we believed that the precision and accuracy of our experimental setup could satisfy the requirements for the measurement of vapor pressure of HCFO-1233xf. The vapor pressures of HCFO-1233xf were measured in a temperature range from (263 to 373) K with vapor pressures from (43 to 1139) kPa, and 99 vapor pressure data were obtained. All the measurement results are shown in Table 2. The experimental data were correlated by Antoine equation ln(P /kPa) = A −
B (T /K) + C
Figure 2. Absolute deviations of pressures between experimental Pexp and calculated Pcalc by the Antoine equation, eq 1: ▲, ref 5.
(1)
The parameters A, B, and C of eq 1 were determined as A = 15.11743, B = 3069.729, and C = 7.14892. The normal temperature of boiling-point was calculated from eq 1 to be 285.23 K. The present data were also correlated by the Wagner equation with four parameter ln(P /Pc) = (A1τ + A 2 τ1.5 + A3τ 3 + A4 τ 6)Tc/T , τ = (Tc − T )/Tc
(2)
the critical temperature Tc and pressure Pc were estimated to be 439.98 K and 3322.01 kPa, respectively, by using Marrero and Pardillo’s method.7 The parameters A1, A2, A3, and A4 were determined to be −4.19560, −4.84497, +5.40056, and −6.39558, respectively. The acentric factor of HCFO-1233xf was calculated from eq 2 to be ω = 0.1873. The deviations of pressure was defined as dP =
|dP | =
1 n
1 n
Figure 3. Relative deviations of pressures between experimental Pexp and calculated Pcalc by the Antoine equation, eq 1: ▲, ref 5.
n
∑ [(Pexp − Pcal)/Pexp]100 i=1
(3)
n
∑ [|(Pexp − Pcal)/Pexp|]100 i=1
(4)
The parameters n in eq 4 is the amount of experimental data. The deviations for the Antoine equation were determined: dP = 0.0070 % and abs (dP) = 0.41 %. The error distribution of the Antoine equation and some points reported in the US patent application by Pham et.al5 are shown in Figure 2 and 3. The absolute deviations of experimental pressures from the correlation by the Antoine equation were determined to be usually less than ± 2 kPa and always less than ± 5 kPa. At the same time, the relative deviations were distributed usually within ± 0.5 % and always within ± 1.0 %. The calculated values also agreed well with those reported in the patent.5 Therefore, the precision and accuracy of the above Antoine constants is enough to be employed for development and design of the chemical engineering process. The deviations for the Wagner equation were determined: dP = −0.0004 % and abs(dP) = 0.40 %. The error distribution of the Wagner equation is shown in Figure 4 and 5. The
Figure 4. Absolute deviations of pressures between experimental Pexp and calculated Pcalc by the Wagner equation, eq 2.
absolute deviations for Wagner equation were distributed usually within ± 2 kPa and always within ± 6 kPa. The relative deviations were determined to be consistent within ± 1.0 % except one point within ± 1.2 %. 2309
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Figure 5. Relative deviations of pressures between experimental Pexp and calculated Pcalc by the Wagner equation, eq 2.
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CONCLUSIONS The data of vapor pressure with ninety-nine points were obtained for HCFO-1233xf at temperature from (263 to 373) K with pressure from (43 to 1139) kPa. The standard uncertainties of measured temperature and pressure were ± 10 mK and ± 1.2 kPa, respectively. To verify the reliability of our experimental setup, vapor pressure data of HFC-245fa were also taken at the same temperature from (263 to 373) K, and good consistency with Wagner equation was found. The acentric factors and normal boiling points of HCFO-1233xf were also determined.
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AUTHOR INFORMATION
Corresponding Author
*Fax: +86-29-88291213. Tel: +86-29-88291213. E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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REFERENCES
(1) The European Parliament and the Council of the European Union. Directive 2006/40/EC relating to emissions from air conditioning systems in motor vehicles and amending Council Directive 70/156/EEC. Off. J. Eur. Union, 2006, 161, 12−18. (2) Kano, Y.; Kayukawa, Y.; Fujii, K.; Sato, H. Ideal-gas Heat capacity for 2,3,3,3-tetrafluoropropene (HFO-1234yf) determined from speedof-sound measurements. Int. J. Thermophys. 2010, 31, 2051−2058. (3) Mukhopadhyay, S.; Light, B. A.; Fleming, K. M.; Phillips, S. D.; Dubey, R. K. Gas phase synthesis of 2,3,3,3-tetrafluoro-1-propene from 2-chloro-3,3,3-trifluoro-1-propene. US 20090124837 A1, 2009. (4) Kopkalli, H.; Chiu, Y.; Tung, H. S. Method for producing fluorinated organic compounds. US 20090287026 A1, 2009. (5) Pham, H. T.; Singh, R. R.; Tung, H., Pokrovski, K. A.; Merkel, D. C. Azeotrope-like compositions of 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf) and 2-chloro-1,1,1,2-tetrafluoropropane (HCFC244bb). US 20090242832 A1, 2009. (6) Wang, Z.; Duan, Y. Vapor pressures of 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea). J. Chem. Eng. Data 2004, 49, 1581−1585. (7) Poling, B. E.; Prausnitz, J. M.; O’Connell, J. P. The Properties of Gases and Liquids, 5th ed.; McGraw-Hill: New York, 2001.
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