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May 28, 2015 - However, to our knowledge, no experimental data have been published on the thermophysical properties of 1,1,1-trifluoro-2,3-dichloropro...
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Measurements of Density, Viscosity, and Vapor Pressure for 1,1,1Trifluoro-2,3-dichloropropane Wei Zhang, Zhi-qiang Yang, Jing Lu, Juan Zhao, Wei Mao, and Jian Lu* Xi’an Modern Chemistry Research Institute, Xi’an, Shaanxi 710065, People’s Republic of China ABSTRACT: The density and viscosity were measured in the temperature range of (273.15 to 333.15) K at atmospheric pressure, and the vapor pressure was measured at temperatures from (293.59 to 400.80) K for 1,1,1-trifluoro-2,3-dichloropropane. The expanded uncertainties in temperature, density, viscosity, and pressure measurements were estimated to be less than 20 mK, 0.0005 g·cm−3, 0.006 mPa·s and 1.2 kPa, respectively. A total of 31 density experimental points were obtained with 31 viscosity experimental points and 58 vapor pressure experimental points. Temperature-dependence correlation equations for the density, viscosity, and vapor pressure were proposed.

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INTRODUCTION Recently, 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf) was identified as a potential alternative for 1,1,1,2-tetrafluoroethane (HFC-134a) in automobile air conditioners1 because of its low global warming potential (GWP) of 4 and thermodynamic properties similar to 1,1,1,2-tetrafluoroethane. Thus, the manufacture of 2,3,3,3-tetrafluoro-1-propene has received much attention in the chemical industry. In one favorable commercial process,2−4 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) is used as an important raw material or intermediate for manufacture of 2,3,3,3-tetrafluoro-1-propene. As the important thermophysical properties, the density, viscosity, and vapor pressure of the fluid are indispensably foundational data for design and evaluation of transport and separation processes. However, to our knowledge, no experimental data have been published on the thermophysical properties of 1,1,1-trifluoro-2,3-dichloropropane in the open literature, although a lot of data have been reported for the thermophysical properties of 2,3,3,3-tetrafluoro-1-propene.5−17 In this work, the density and viscosity of 1,1,1-trifluoro-2,3dichloropropane were measured in the temperature range from (273.15 to 333.15) K at atmospheric pressure, and the vapor pressure was measured at temperature from (293.59 to 400.80) K. The relationships of the density, the viscosity, and the vapor pressure with the temperature were correlated.

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pressure, the sample was degassed in liquid nitrogen to eliminate the effect of gaseous impurities. Apparatus. Measurements of density and viscosity were performed using an Anton Paar SVM 3000 Stabinger viscometer-densimeter. The expanded uncertainty of temperature was 20 mK in measurement range of the apparatus. The absolute expanded uncertainties of the density and the viscosity were less than 0.0005 g·cm−3 and 0.0060 mPa·s by calibration using the standard fluid SHL115 (SH Calibration Service GMbH, Austria) in the range of the studied temperatures. Measurement of vapor pressure was carried out using a Burnett apparatus that has been described previously.18 The temperature and pressure were measured by a platinumresistance thermometer (Yunnan Instrument, China; No.4349) and an absolute pressure sensor (GE PMP4051, China). The total expanded uncertainties of the vapor pressure measurements were estimated less than 20 mK for temperature and 1.2 kPa for pressure at a confidence level of approximately 95% (k = 2).

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RESULTS AND DISCUSSION Density. Measurement of density of 1,1,1-trifluoro-2,3dichloropropane was carried out in the temperature range from (273.15 to 333.15) K at atmospheric pressure. The experimental data obtained are presented in Table 1. The experimental density data were regressed using the following temperature-dependence equation

EXPERIMENTAL SECTION

ρ /(g·cm−3) = A1 + A 2 (T /K)

Materials. The sample of 1,1,1-trifluoro-2,3-dichloropropane was supplied by Weihai New Era Chemical Co. Ltd., China. Its purity was analyzed with a gas chromatograph (Shimadzu GC-2010, Japan) equipped with a flame ionization detector and a capillary column (PLOT Al2O3 S, Agilent model 19091P-S33). The result indicated that the mass purity of the sample was better than 0.999. Before the experiment of vapor © XXXX American Chemical Society

(1)

where ρ is the density, T is the temperature, A1 and A2 are fitted parameters. The regressed parameters of eq 1 are summarized Received: November 21, 2014 Accepted: May 15, 2015

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DOI: 10.1021/je5010593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Experimental Density of 1,1,1-Trifluoro-2,3-dichloropropane at P = 0.1 MPaa

a

T

ρ

T

ρ

T

ρ

T

ρ

K

g·cm−3

K

g·cm−3

K

g·cm−3

K

g·cm−3

273.15 275.15 277.15 279.15 281.15 283.15 285.15 287.15

1.5008 1.4968 1.4931 1.4893 1.4853 1.4813 1.4776 1.4739

289.15 291.15 293.15 295.15 297.15 299.15 301.15 303.15

1.4701 1.4663 1.4623 1.4584 1.4545 1.4506 1.4466 1.4427

305.15 307.15 309.15 311.15 313.15 315.15 317.15 319.15

1.4387 1.4347 1.4308 1.4268 1.4228 1.4188 1.4148 1.4108

321.15 323.15 325.15 327.15 329.15 331.15 333.15

1.4067 1.4027 1.3986 1.3945 1.3904 1.3863 1.3823

Expanded uncertainties (k = 2) are U(T) = 0.02 K and U(ρ) = 0.0005 g·cm−3.

are shown in Figure 2. The relative deviations of measurements from eq 1 were determined to be within ± 0.06 %, whereas the

in Table 2. The average absolute relative deviation (AARD) of the correlation was 0.025%. The AARD is defined as follows: Table 2. Parameters for Equations equations eq 1 eq 3 eq 4 eq 5

parameters A1 2.0404 B1 −4.54269 C1 18.56000 D1 −6.25542

1 AARD = n

n

∑ i=1

A2 1.9731 × 10−3 B2 1.28508 × 103 C2 −6.771567 × 103 D2 −2.16585

(Yexpt − Ycalc) Yexpt

C3 140.0273 D3 4.65713

D4 5.15577

× 100% i

(2)

where n is the number of experimental points, Y symbolizes the thermophysical property of density (ρ), viscosity (η), or vapor pressure (P), the subscripts expt and calc represent the experimental data and calculated value from the correlative equations, respectively. Figure 1 shows the experimental data and calculated values of density versus temperature and the relative deviations of density between the measured data and those calculated by eq 1

Figure 2. Relative deviations between experimental densities (ρexpt) and densities calculated from eq 1 (ρcalc).

maximum deviation was found to be −0.0008 g·cm−3. The results reveal that eq 1 can represent the experimental density data very well. Viscosity. The viscosity of 1,1,1-trifluoro-2,3-dichloropropane was measured in the temperature range from (273.15 to 333.15) K at atmospheric pressure. The experimental data are shown in Table 3 and fitted by the following temperaturedependence equation B2 ln(η /(mPa· s)) = B1 + (T /K) (3) where η is the viscosity, T is the temperature, B1 and B2 are fitted parameters. The fitted viscosity parameters of 1,1,1-trifluoro-2,3-dichloropropane are summarized in Table 2. The AARD of the correlation was 0.410%. Figure 3 displays the experimental viscosity data and calculated values versus temperature. Figure 4 shows the relative deviations for viscosity data calculated from eq 3. From Figures 3 and 4, it can be seen that eq 3 can predict the experimental data of viscosity very well. The relative deviations of measurements from eq 3 were determined to be consistent within ± 1.0 % except one point within ± 1.5 %, whereas the maximum deviation was 0.0071 mPa·s. Vapor Pressure. The vapor pressure of 1,1,1-trifluoro-2,3dichloropropane was measured in the temperature range from

Figure 1. Density of 1,1,1-trifluoro-2,3-dichloropropane as a function of temperature: ▲, experimental liquid densities; , calculated densities using eq 1. B

DOI: 10.1021/je5010593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. Experimental Viscosity of 1,1,1-Trifluoro-2,3-dichloropropane at P = 0.1 MPaa

a

T

η

T

η

T

η

T

η

K

mPa·s

K

mPa·s

K

mPa·s

K

mPa·s

273.15 275.15 277.15 279.15 281.15 283.15 285.15 287.15

1.174 1.136 1.097 1.063 1.028 0.997 0.967 0.937

289.15 291.15 293.15 295.15 297.15 299.15 301.15 303.15

0.911 0.882 0.855 0.829 0.804 0.782 0.761 0.738

305.15 307.15 309.15 311.15 313.15 315.15 317.15 319.15

0.715 0.693 0.674 0.656 0.641 0.626 0.610 0.593

321.15 323.15 325.15 327.15 329.15 331.15 333.15

0.578 0.567 0.556 0.545 0.533 0.521 0.511

Expanded uncertainties (k = 2) are U(T) = 0.02 K and U(η) = 0.006 mPa·s.

Table 4. Experimental Vapor Pressure of 1,1,1-Trifluoro-2,3dichloropropanea

Figure 3. Viscosity of 1,1,1-trifluoro-2,3-dichloropropane as a function of temperature: ▲, experimental liquid viscosities; , calculated viscosities using eq 3.

T

P

T

P

K 293.59 295.22 297.85 299.71 301.48 302.81 304.77 306.67 308.94 310.84 312.83 314.86 316.73 318.85 320.87

T

P

T

P

kPa

K

kPa

K

kPa

K

kPa

19 20 22 24 25 26 28 30 32 35 37 39 42 45 48

322.92 324.95 326.95 327.71 328.96 330.96 332.97 334.96 336.92 337.73 339 341.25 343 345.02 345.61

51 54 58 60 61 65 69 73 78 80 83 89 93 99 102

347 348.98 350.9 352.86 354.88 356.76 358.8 360.79 362.69 364.7 366.7 368.69 370.94 372.76 374.73

105 111 118 124 132 139 147 155 162 171 181 191 203 212 224

376.83 378.96 380.82 382.86 384.8 386.91 389.07 391.28 392.91 394.91 396.85 398.99 400.8

236 249 261 274 287 302 318 335 348 365 381 400 415

a

Expanded uncertainties (k = 2) are U(T) = 0.02 K and U(P) = 1.2 kPa.

The regressed parameters of eq 4 are provided in Table 2, and the calculated vapor pressures are shown in Figure 5. The AARD between experimental vapor pressure and calculated values was 0.531 %. The relative deviations from eq 4 are shown in Figure 6. The relative deviations of measurements

Figure 4. Relative deviations between experimental viscosities (ηexpt) and viscosities calculated from eq 3 (ηcalc).

(293.59 to 400.80) K. The results are listed in Table 4 and fitted by the Antoine equation ln(P /kPa) = C1 +

C2 (T /K) + C3

(4)

Figure 5. Vapor pressures of 1,1,1-trifluoro-2,3-dichloropropane as a function of temperature: ▲, experimental vapor pressure; , calculated vapor pressure using eq 4.

where P is the vapor pressure, T is the temperature, C1, C2, and C3 are Antoine constants. C

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: +86-29-88291213. Tel.: +86-29-88291213. Funding

The authors want to acknowledgment financial support from the Key Scientific and Technological Innovation Special Project of Shaanxi “13115” (Grant No. 2010ZDKG-90). Notes

The authors declare no competing financial interest.

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(1) Minor, B.; Spatz, M. HFO-1234yf low GWP refrigerant update. International refrigeration and air conditioning conference; Purdue University: West Lafayette, IN, 2008; Paper 937, retrieved online at http://docs.lib.purdue.edu/iracc/937. (2) Wendlinger, L.; Pigamo, A.; Deur-Bert, D. Catalytic gas phase fluorination of 243bd to 1234yf. U.S. Patent 8207384, June 26, 2012. (3) Smith, J. W.; McGuiness, C. E.; Sharratt, A. P. Process for the preparation of 2,3,3,3- tetrafluoropropene. U.S. Patent 8536388, September 17, 2013. (4) Smith, J. W.; Mcguiness, C. E.; Sharratt, A. P. Process for the preparation of 2,3,3,3-tetrafluoropropene. U.S. Patent 8697923, April 15, 2014. (5) 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. (6) Perkins, R. A.; Huber, M. L. Measurement and correlation of the thermal conductivity of 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) and trans-1,3,3,3-tetrafluoropropene (R1234ze(E)). J. Chem. Eng. Data 2011, 56, 4868−4874. (7) Tanaka, K.; Higashi, Y.; Akasaka, R. Measurements of the isobaric specific heat capacity and density for HFO-1234yf in the liquid state. J. Chem. Eng. Data 2010, 55, 901−903. (8) Nicola, G. D.; Polonara, F.; Santori, G. Saturated pressure measurements of 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf). J. Chem. Eng. Data 2010, 55, 201−204. (9) Nicola, C. D.; Nicola, G. D.; Pacetti, M.; Polonara, F.; Santori, G. P-V-T behavior of 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf) in the vapor phase from (243 to 373) K. J. Chem. Eng. Data 2010, 55, 3302− 3306. (10) Meng, X.; Qiu, G.; Wu, J.; Abdulagatov, I. M. Viscosity measurements for 2,3,3,3-tetrafluoroprop-1-ene (R1234yf) and trans1,3,3,3-tetrafluoropropene (R1234ze(E). J. Chem. Thermodyn. 2013, 63, 24−30. (11) Fedele, L.; Bobbo, S.; Groppo, F.; Brown, J. S.; Zilio, C. Saturated pressure measurements of 2,3,3,3-Tetrafluoroprop-1-ene (R1234yf) for reduced temperatures ranging from 0.67 to 0.93. J. Chem. Eng. Data 2011, 56, 2608−2612. (12) Richter, M.; McLinden, M. O.; Lemmon, E. W. Thermodynamic properties of 2,3,3,3- tetrafluoroprop-1-ene (R1234yf): vapor pressure and p-ρ-T measurements and an equation of state. J. Chem. Eng. Data 2011, 56, 3254−3264. (13) Akasaka, R. Viscosity correlation for 2,3,3,3-tetrafluoropropene (HFO-1234yf) based on the extended corresponding states model. J. Therm. Sci. Technol. 2010, 5, 200−205. (14) Cousins, D. S.; Laesecke, A. Sealed gravitational capillary viscometry of dimethyl ether and two next-generation alternative refrigerants. J. Res. Natl. Inst. Stand. Technol. 2012, 117, 231−256. (15) Tanaka, K.; Higashi, Y. Thermodynamic properties of HFO1234yf (2,3,3,3- tetrafluoropropene). Int. J. Refrig. 2010, 33, 474−479. (16) Klomfar, J.; Součková, M.; Pátek, J. Liquid-phase p−ρ−T data for 2,3,3,3-tetrafluoro- prop-1-ene (R-1234yf) and 1,1,2,3,3,3-Hexafluoroprop-1-ene (R-1216) at temperatures from (208 to 353) K under pressures up to 40 MPa. J. Chem. Eng. Data 2011, 57, 3283− 3289.

Figure 6. Relative deviations between experimental pressures (Pexpt) and pressures calculated from the fited equation (Pcalc): □, eq 4; ▲, eq 5.

from eq 4 were found to be mostly within ± 1.5 % with two points within ± 2.0 % at lower temperatures, but the absolute deviations were less than ± 4.6 kPa. Equation 4 could basically satisfy the requirements for application in the chemical engineering. The normal boiling point derived from eq 4 was calculated to be Tb of 345.58 K. In addition, a Wagner equation for 1,1,1-trifluoro-2,3dichloropropane was fitted ⎛ P ⎞ (D τ + D2τ1.5 + D3τ 3 + D4 τ 6)Tc ln⎜ ⎟ = 1 T ⎝ Pc ⎠

REFERENCES

(5)

where P is vapor pressure in kPa, Pc is the critical pressure, τ is the dimensionless temperature defined by τ = (Tc − T)/Tc, T is the temperature, the critical temperature Tc = 520.73 K and pressure Pc = 3443.98 kPa were estimated by using Marrero and Pardillo’s method,19 the regressed parameters D1, D2, D3, and D4 are provided in Table 2. The AARD of eq 5 was 0.488 %. Figure 6 shows also the relative deviations from eq 5. The relative deviations of pressure between experimental data and those calculated by eq 5 were found to be consistent within ± 1.0 % with six points within ± 1.7 %, whereas the maximum deviation was −3.4 kPa. The acentric factor of 1,1,1-trifluoro2,3-dichloropropane was calculated from eq 5 to be ω = 0.3048.

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CONCLUSIONS A total of 31 experimental points for density and 31 experimental points for viscosity were obtained in the temperature range of (273.15 to 333.15) K at atmospheric pressure, and 58 experimental points for vapor pressure were obtained in the temperature range from (293.59 to 400.80) K for 1,1,1-trifluoro-2,3-dichloropropane. The expanded uncertainties of measured temperature, density, viscosity, and pressure were 20 mK, 0.0005 g·cm−3, 0.006 mPa·s, and 1.2 kPa at a confidence level of approximately 95 %, respectively. The relationships of the density, viscosity, and vapor pressure with the temperature were correlated. The normal boiling point and acentric factor of 1,1,1-trifluoro-2,3-dichloropropane were also determined. D

DOI: 10.1021/je5010593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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(17) Fedele, L.; Brown, J. S.; Colla, L.; Ferron, A.; Bobbo, S.; Zilio, C. Compressed liquid density measurements for 2,3,3,3-tetrafluoroprop1-ene (R1234yf). J. Chem. Eng. Data 2012, 57, 482−489. (18) Zhang, W.; Yang, Z.; Lu, J.; Lu, J. Vapor pressures of 2-chloro3,3,3-trifluoropropene (HCFO-1233xf). J. Chem. Eng. Data 2013, 58, 2307−2310. (19) 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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DOI: 10.1021/je5010593 J. Chem. Eng. Data XXXX, XXX, XXX−XXX