Physical Properties of HCFO-1233zd(E) - Journal of Chemical

Article pubs.acs.org/jced

Physical Properties of HCFO-1233zd(E) Paper presented at the 18th Symposium on Thermophysical Properties, Boulder, CO, June 24 to 29, 2012. Ryan J. Hulse, Rajat S. Basu,* Rajiv R. Singh, and Raymond H. P. Thomas Honeywell International Inc., 20 Peabody St., Buffalo, New York 14210, United States ABSTRACT: A new low global warming potential (GWP) fluid hydrochlorofluoroolefin trans-isomer of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) has been developed in our laboratory. HCFO-1233zd(E) has a very short atmospheric lifetime of 26 days and a global warming potential (GWP) of less than 5 (Wong et al., http://www.honeywell-solsticelba.com. product-info/environmental-regulatory/#atmospheric-impact, 2012). This makes it an excellent environmentally friendly candidate for many applications including refrigeration, foam expansion agents, and as solvents. In this work we have presented our measurements of physical properties like the boiling point, critical temperature, vapor pressure, liquid density, and surface tension of HCFO-1233zd(E). We have also provided our calculated ideal gas heat capacity at constant pressure using quantum mechanical theory. Temperature-dependent properties are correlated with standard forms of equations and described in the paper.

1. INTRODUCTION In 1970 Molina and Rowland2 discovered the Earth’s stratospheric ozone depletion by chlorofluorocarbons (CFCs) and various other halogenated compounds which brought about a big change in the use of CFCs, as refrigerants, as foam expansion agents, as cleaning solvents, and in many other applications. CFCs used to be a workhorse in some of these industries. This led to a worldwide activity in the development of new generation of compounds to replace CFCs. The industry transitioned from chlorofluorocarbons (CFCs) → hydrochlorofluorocarbons (HCFCs) → hydrofluorocarbons (HFCs). As these fluids were adopted and being used, another major environmental problem ensued, the warming of the Earth due to the greenhouse gases. Various pressures were brought to bear on the market to solve this problem including the enactment by several countries of laws to control emissions of these fluids. Now new classes of fluids were required to have adequate stability to survive the conditions of typical applications such as refrigeration but at the same time required to have a shorter atmospheric lifetime so that the contribution to global warming is small. One of the finding is that certain unsaturated compounds were uniquely suited to satisfy this description while remaining effective and safe. The focus of this work is to explore these certain unsaturated fluorinated compounds designated as hydrofluoroolefins (HFOs) and hydrocholorofluoroolefins (HCFOs). Both of these sets of compounds have been shown to have an extremely short atmospheric lifetime due to their reactivity with atmospheric hydroxyl radicals (Papadimitriou et al.3). The short atmospheric lifetime that is associated with these HFOs © 2012 American Chemical Society

and HCFOs drives the low GWP of these classes of compounds. In the past, similar work has been published on HFO-2,3,3,3-tetrafluoropropene (HFO-1234yf) and HFO1,3,3,3-tetrafluoropropene (HFO-1234ze) (Hulse et al.4) which are used to replace some of the HFCs such as 1,1,1,2tetrafluoropropane (HFC-134a), which has higher global warming potential (GWP) in automotive air conditioning, and 1,1,3,3,3-pentafluoropropane (HFC-245fa) in foam expansion agents and as solvents. The unsaturated chloroolefin compound which has been discovered for many of the uses is 1chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)). This has an extremely short atmospheric lifetime of 26 days1 and a GWP of less than 5 compared to a GWP of 950 for compounds such as HFC-245fa and which has an atmospheric lifetime of 7.6 years (Nelson et al.5). Despite such a short atmospheric lifetime it is extremely stable under potential use conditions. Although it has chlorine in the molecule, HCFO-1233zd(E) has a negligible ozone depletion potential. In this paper, we are going to describe thermophysical properties of HCFO-1233zd(E) measured in our laboratory. The properties that are typically required for system evaluations are vapor pressure, density, viscosity, ideal gas heat capacity, and also surface tension.

2. EXPERIMENTAL SECTION 2.1. Critical Constants. The critical temperature of HCFO1233zd(E) was determined by visual observation of the Received: July 12, 2012 Accepted: November 9, 2012 Published: November 21, 2012 3581

dx.doi.org/10.1021/je300776s | J. Chem. Eng. Data 2012, 57, 3581−3586

Journal of Chemical & Engineering Data

Article

Table 2. Vapor Pressure of HCFO-1233zd(E)a

disappearance and reappearance of the vapor−liquid meniscus as a high-pressure glass tube containing HFO-1233zd(E) was heated and cooled (Hulse et al.4). Initially a high-pressure glass tube was charged with a measured amount of degassed HCFO1233zd(E). The tube was then heated in an oil bath until the disappearance of the vapor−liquid meniscus was observed. If this disappearance occurred above or below the center of the glass tube, another tube was prepared with a modified mass until the mass corresponding to critical density was charged into the tube when the vapor−liquid meniscus disappears at the middle of the tube. The critical temperature was determined to be 438.75 K. The uncertainty in the measurement is estimated to be ± 0.05 K. The critical pressure was determined by extrapolating the measured vapor pressure data to the critical temperature. From the critical temperature and the vapor pressure correlation shown in eq 1 the critical pressure has been determined to be 3772.1 kPa (547.1 psia). The critical pressure is extrapolated from measurements away from critical temperature and therefore may have larger uncertainties. So this value has to be used with caution until critical pressure is measured experimentally. The purity of the substance in all the property measurements is given in Table 1. All of the impurities have not been clearly identified and therefore cannot be provided.

T/K

P/kPa

263.09 272.95 273.10 282.95 283.08 293.05 293.08 302.85 303.01 312.25 312.93 321.85 323.00 332.93 342.92 352.84

29.85 44.51 47.57 71.41 72.74 107.99 106.52 148.21 152.10 203.33 210.08 279.37 282.13 382.66 502.28 641.35

The uncertainty in temperature measurement is ± 0.001 °C, and the uncertainty in pressure measurement is estimated to be ur(P) = 0.01.

a

Table 1. Critical Propertiesa properties

values

critical temperature (K) critical pressure (estimated) (kPa) purity of the substance (mass fraction)

438.75 3772.1 0.99

The critical temperature measurement uncertainty is ± 0.05 °C, and the critical pressure measurement uncertainty is higher and estimated to be between (20 and 30) kPa due to extrapolation from vapor pressure data taken at lower temperatures.

a

Figure 1. Plot of P/kPa of the experimental vapor pressure of HCFO1233zd(E) as a function of T/K. The solid line shows P/kPa calculated using eq 1, and the solid dot indicates experimental points.

2.2. Vapor Pressure. The vapor pressure of HCFO1233zd(E) was measured using a MKS pressure transducer (model 628RCTBE1B) that was heated to 100 °C to avoid any condensation (Hulse et al.4). A cylinder of degassed HFO1233zd(E) fitted with the heated MKS pressure transducer was placed in a constant temperature bath. The temperature of the bath was measured using a platinum resistance thermometer which has an uncertainty of ± 0.001 °C. The MKS pressure transducer was calibrated using a dead weight tester and determined to have a combined measurement uncertainty of about ur(P) = 0.01. The measured vapor pressure values of HCFO-1233zd(E) are given in Table 2. The saturated vapor pressure has been correlated using the Antoine vapor pressure equation (Poling et al.6) which is shown in eq 1. The vapor pressure equation is given by, 3161.9 (1) T Here P is pressure in kPa, and T is temperature in K. Figure 1 shows the plot of experimental and measured vapor pressure of HCFO-1233zd(E), and Figure 2 shows the deviation plot of the experimental and measured vapor pressure in percentages. The deviation between experimental and calculated vapor pressure is found to be outside the range of experimental uncertainties in this case. The reason for this wide difference cannot be ascertained very well. The purity of the samples were about 99 wt %, and authors attribute the presence of other ln(P) = 22.35 −

Figure 2. Relative deviation ΔP/Pexpt·100 = {(Pexpt − Pcalc)/Pexpt}·100 of experimental vapor pressure Pexpt, as a function of temperature T/K; Pcalc is calculated using eq 1. The solid dots are the relative deviations of data points.

impurities as one contributing factor to the large deviation between experimental data and Antoine equation. All of the impurities have not been clearly determined in this case. 2.3. Liquid Density. The liquid density was initially determined using standard density floats which have a reported 3582



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uncertainty of ± 0.2 kg·m−3. The float technique has been discussed by Basu and Wilson7 in an earlier paper. The density values reported in Table 3 below were measured over a temperature range of (243.34 to 293.21) K using a vibrating tube densitometer (Tropea et al.8) which was calibrated using HFC-134a. Table 3. Saturated Liquid Density of HCFO-1233zd(E)a T/K

ρ/kg·m−3

243.34 243.70 248.07 251.12 253.56 255.66 263.36 271.16 273.17 283.26 290.16 291.98 293.21

1384.7 1384.0 1371.4 1367.4 1362.5 1360.3 1341.3 1323.7 1319.7 1296.5 1280.2 1276.0 1273.4

Figure 4. Relative deviation Δρ/ρ·100 = {(ρexpt − ρcalc)/ρexpt}·100 of experimental densities ρexpt as a function of temperature T/K for HCFO-1233zd(E); ρcalc indicates calculated values of ρ using eq 2, and the solid dot indicates relative deviations of data points.

Gaussian 09 program, based on the density functional theory. The Becke, three-parameter, Lee−Yang−Parr (B3LYP) (Becke10) density functional with 6-31+G** basis was used in the calculation. As recommended by Irikura11 a scaling factor of 0.964 was used for the frequencies. Heat capacity calculations were done following Xu et al.12 Ideal gas heat capacity values calculated using the method described above are shown in Table 4 below. The last column in the Table 4 shows the deviation in percentages between calculated and fitted values.

a The uncertainty in temperature measurement is ± 0.001 °C, and the uncertainty in measured density ur(ρ) = 0.001.

The saturated liquid density has been correlated to the DIPPR liquid density equation9 as follows 129.755 ρL = 0.28571 T ) (2) 0.26713(1 + (1 − 438.75 )

Table 4. Ideal Gas Heat Capacity of HFO-1233zd(E)

−3

here ρL is the saturated liquid density in kg·m and T is in K. Figure 3 shows the plots of measured and calculated liquid

T/K

lCidp /J·mol−1·K−1

100 200 298.15 300 400 500 600 700 800 900 1000

57.01 82.57 105.66 106.07 125.63 140.70 152.09 160.80 167.63 173.10 177.57

Ideal gas heat capacity values were correlated to a polynomial in absolute temperature, and the equation is given below. Cpid = 32.44258 + 0.22355T + 3.19642·10−4T 2

Figure 3. Plot of ρ/kg·m−3 of HCFO-1233zd(E) vs T/K. The solid line indicates ρ/kg·m−3 calculated using eq 2, and the solid dot indicates experimental points.

− 1.10771·10−6T 3 + 1.05332·10−9T 4 − 3.43667 ·10−13T 5

(3)

Here Cidp is the −1 −1

ideal gas heat capacity of HCFO-1233zd(E) in J·mol ·K , and T is temperature in K. Ideal gas heat capacity values and the deviation plots are shown in Figures 5 and 6. The polynomial correlation represents the calculated data quite well. 2.5. Dynamic Liquid Viscosity. The dynamic liquid viscosity was measured using a specially designed capillary tube method by Geller,13 and the values are given in Table 5. The correlation of the experimental dynamic liquid viscosity data is given by eq 4 where η is the dynamic liquid viscosity in μPa·s and temperature is in K.

density, and Figure 4 shows the deviation plot between calculated and measured values. In this case most of the measured values fell well within experimental uncertainties. This fitting uses a nonlinear fitting routine in Minitab software. Rounding-off the exponent from 0.28571 to 0.29 will increase the AAD by 6, so rounding-off of the exponent should not be done. 2.4. Ideal Gas Heat Capacity. The ideal gas heat capacity has been calculated from the vibrational energies of HFO1233zd(E) using quantum mechanical methods. The vibrational frequencies of HFO-1233zd(E) were obtained using 3583



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Figure 7. Plot of η/μPa·s viscosity of HCFO-1233zd(E) as a function of T/K. The solid line indicates η/μPa·s calculated using eq 4, and the solid dot indicates experimental points.

Figure 5. Plot of ideal gas heat capacity Cidp /J·mol−1·K−1 of HCFO1233zd(E) as a function of T/K. The solid line indicates Cidp / J·mol−1·K−1 calculated using eq 3, and the solid dot indicates Cpid/ J·mol−1·K−1 estimated using Gaussian 09.

Figure 8. Relative deviation Δη/η·100 = {(ηexpt − ηcalc)/ηexpt}·100 as a function of T/K. ηcalc is from eq 4, and the solid dot indicates relative deviations of data points.

Figure 6. Relative deviation ΔCidp /Cidp ·100 = {(Cidp (Gaussian) − Cidp (calculated)/Cidp (Gaussian)}·100 as a function of T/K. Here Cidp / J·mol−1·K−1, the ideal gas heat capacity of HCFO-1233zd(E), is calculated using eq 3, and the solid dot indicates relative deviations of data points.

are shown in Table 6. No attempt was made to develop any correlation equation for surface tension as a function of temperature because of only a few measured data points in this case.

Table 5. Compressed Dynamic Liquid Viscosity η of HFO1233zd(E)a T/K

P/kPa

η/μPa·s

270.24 292.03 314.25 336.37 353.52 379.56

100 150 300 500 800 1350

705 506 385.1 294 236.9 176.3

Table 6. Surface Tension of HCFO-1233zd(E)a 273.15 298.15 323.15

16.48 12.68 9.01

The uncertainty in temperature measurement is ± 0.01 °C, and the uncertainty in surface tension measurement is ur(ST) = 0.01.

The uncertainty in temperature measurement is ± 0.01 °C, and the uncertainty in viscosity measurement is ur(η) = 0.012.

7683.45 (T + 458.66)

σ/N·m−1·103

a

a

ln(η) = −10.8989 +

T/K

2.7. HCFO-1233zd(E) Performance. HCFO-1233zd(E) is beneficial for use as a solvent and also as an expansion agent in thermal insulation foams. In this paper we are going to describe the performance of HCFO-1233zd(E) as a cleaning solvent. The miscibility test was done where equal parts of solvent and oils are mixed together, and visual observation was made to see if the soils and HCFO-1233zd(E) remained in a single phase, indicating that the oils were completely dissolved in the solvent. In all cases shown in Table 7 the solvent looked clear indicating complete dissolution of oils in solvent. This is an initial mode of testing to check how well the solvent performs in dissolving the oils. Some of these results have been presented earlier in Basu et al.15 and are included here for completeness.

(4)

Figure 7 shows plots of experimental and calculated dynamic liquid viscosity versus temperature, and Figure 8 shows the deviation plots of experimental and calculated dynamic viscosity of HFO-1233zd(E). The correlated equation represents most of the experimental data within experimental uncertainty. 2.6. Surface Tension. Limited surface tension measurements for HCFO-1233zd(E) were done using the capillary rise method. The capillary rise system is commonly used to measure surface tension as reported by Lin et al.14 The measured surface tension (σ) values in the units of N·m−1·103 3584



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shown excellent solubility and cleaning capability for a number of oils.

Table 7. Oil Dissolution in Solvents oils

solubility

mineral oil solder flux refrigerant oil silicone lubricant

miscible miscible miscible miscible

■

Corresponding Author

*Phone: (716) 827 6231. Fax: (716) 827 6373. E-mail: rajat. [email protected].

HCFO-1233zd(E) has miscibility properties similar to some of the chlorinated solvents which are indeed very good solvents but which are also very toxic. Oils such as perfluorinated lubricants and polyalkylene glycols all showed solubility in 1233zd(E) at greater than 10 wt %. In the next step, we did an evaluation of how good the solvent is in cleaning parts soiled with oils. In these tests we soiled small approximately 2” by 1” stainless steel coupons with various commercial oils used in the field. The coupons were immersed in boiling 1233zd(E) for 2 min and dried in the solvent vapors. This test was performed in small beakers with condenser coils near its lips which emulated conditions similar to lab vapor degreasing equipment. Coupons were visually observed for cleanliness, and weight changes of the coupons were also noted. Cleaning results are given in Table 8 and show

Notes

Although all statements and information contained herein are believed to be accurate and reliable, they are presented without guarantee or warranty of any kind, expressed or implied. Information provided herein does not relieve the user from the responsibility of carrying out its own tests and experiments, and the user assumes all risks and liability for use of the information and results obtained. Statements or suggestions concerning the use of materials and processes are made without representation or warranty that any such use is free of patent infringement and are not recommendations to infringe on any patents. The user should not assume that all toxicity data and safety measures are indicated herein or that other measures may not be required. The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS Authors would like to acknowledge H. Pham for some of the measurements of physical properties, Kane Cook for some of the cleaning performance studies, and Dave Williams and Jim Bowman all of Honeywell International, Inc. for providing some useful application information. The authors would also like to thank Vladimir Geller of TRC for the measurement of liquid viscosity under contract from Honeywell International, Inc.

Table 8. Soil Removal from Coupons Using 1233zd(E) test oil vacuum pump oil cutting oil silicone oil mineral oil

removal/mass fraction

test oil

AUTHOR INFORMATION

removal/mass fraction

0.997

Mil-PRF-83282

1

0.993 0.994 0.998

Mil-PRF-C-81309 VV-D-1078 Nye oil 438

0.988 0.977 0.724

■

that it removed the oils from stainless steel coupons quite well for all of the oils except for one. This demonstrates good degreasing efficacy of the solvent 1233zd(E). Here Mil-PRF-83282 is a hydraulic fluid, and Mil-PRF-C81309 is a corrosion preventative compound used by the miltary in various applications; VV-D-1078 is a silicone-based damping fluid, and Nye oil is a synthetic lubricant.

REFERENCES

(1) Wong, D.; Olsen, S.; Weubbles, D. Preliminary Report: Analyses of CFPs Potential Impact on Atmospheric Ozone. http://www. honeywell-solsticelba.com.product-info/environmental-regulatory/ #atmospheric-impact, 2012. (2) Molina, M. J.; Rowland, F. S. Stratospheric sink for chlorofluoromethanes: chlorine atom-catalysed destruction of ozone. Nature 1974, 249, 810−812. (3) Papadimitriou, V. C.; Talukdar, R. K.; Portmann, R. W.; Ravishankara, A. R.; Burkholder, J. B. 2008 CF3CFCH2 and (Z)CF3CFCHF: temperature dependent OH rate coefficients and global warming potentials. Phys. Chem. Chem. Phys. 2006, 10 (6), 808− 820. (4) Hulse, R. J.; Singh, R. R.; Pham, H. Proceedings of the 17th Thermophysical Properties Conference, Boulder, CO, 2009, paper #178. (5) Nelson, D. D.; Zahnsir, M. S., Jr.; Kolb, C. E.; Magid, H. OH reaction kinetics and atmospheric lifetime estimates for several hydrofluorocarbons. J. Phys. Chem. 1995, 99, 16301−16306. (6) Poling, B. E.; Prausnitz, J. M.; O’Connell; J. P. The Properties of Gases and Liquids, 5th ed.; McGraw-Hill: New York, 2001. (7) Basu, R. S.; Wilson, D. P. Thermophysical Properties of 1,1,1,2Tetrafluoropropane (R-134a). Int. J. Thermophys. 1989, 10 (3), 591− 603. (8) Tropea, C.; Yarin, A. L.; Foss, J. F., Eds. Springer Handbook of Experimental Fluid Mechanics, Vol. 1; Springer-Verlag: Berlin, 2007. (9) Rackett, H. G. Equation of state for saturated liquids. J. Chem. Eng. Data 1970, 15, 514−517. (10) Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648−5652. (11) Irikura, K. K.; Johnson, R. D., III; Kacker, R. N. Uncertainties in Scaling Factors for ab Initio Vibrational Frequencies. J. Phys. Chem. A 2005, 109, 8430−8437.

3. CONCLUSION In summary we have presented in this paper a range of thermophysical properties including the critical properties, vapor pressure, liquid density, ideal gas heat capacity, liquid viscosity and surface tension of HCFO-1233zd(E). Critical temperature was measured and critical pressure was estimated. Vapor pressure, liquid density, liquid viscosity and surface tension were also measured. Except for surface tension these experimentally measured values are correlated to standard equations which are also presented in the paper. Correlation equations represent experimental values well within experimental uncertainty except for vapor pressure. Deviations between experimental and calculated vapor pressure values were found to be larger than estimated experimental uncertainties. The reason for this deviation cannot be ascertained very well. No attempt has been made to correlate surface tension measurements to any correlation equation because of very few data points. Ideal gas heat capacity was calculated using Gaussian 09 software and later correlated to a polynomial equation in absolute temperature. We have also shown application of the compound as a cleaning solvent. It has 3585



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(12) Xu, L.-H.; Andrews, A. M.; Cavanaugh, R. R.; Fraser, G. T.; Irikura, K. K.; Lovas, F. J.; Grabow, J.-U.; Stahl, W.; Crawford, M. K.; Smalley, R. J. Rotational and Vibrational Spectroscopy and Ideal Gas Heat Capacity of HFC 134a (CF3CFH2). J. Phys. Chem. A 1997, 101, 2288−2297. (13) Geller, V. Thermodynamics Research Center, San Francisco, CA. Private Communication. (14) Lin, H.; Duan, Y. Y.; Wang, Z. W. Surface tension measurements of 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) from 254 to 333 K. Fluid Phase Equilib. 2003, 214, 79−86. (15) Basu, R. S.; Hulse, R.; Mercier, D. Paper Presented at the IPCC meeting in San Diego 2012, IPC, Bannockburn, IL, 2012.

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Physical Properties of HCFO-1233zd(E) - Journal of Chemical

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