Preparation of 1,1,1,3,3-pentafluoropropane (HFC-245fa) by using a SbF5-attached catalyst

In this report, a simple process for preparing HFC-245fa through the reaction of 1,1,1,3,3-pentachloropropane (PCP) and anhydrous HF via two-step vapor-phase catalytic fluorination is described. The antimony pentafluoride catalyst was supported on inert porous materials to improve the catalytic activity. The resulting process catalyst not only exhibited high catalytic activity and excellent thermo-stability, but also improved the performance of SbF₅, in terms of hygroscopicity and corrosion.     

Isobaric heat capacities of R245fa and R236fa in liquid phase at temperatures from (315 to 365) K and pressures up to 5.5 MPa

Isobaric heat capacities of compressed liquid 1,1,1,3,3-pentafluoropropane (R245fa) and 1,1,1,3,3,3-hexafluoropropane (R236fa) were measured by scanning calorimetry. The experimental system basically consists of a calvet calorimeter (Setaram C80) and a pressure balance unit. A total of 55 data points for liquid R245fa and 52 data points for liquid R236fa were obtained at temperatures from (315 to 365) K and pressures up to 5.5 MPa. The uncertainties for the heat capacity of R245fa and R236fa were estimated to be (1.8 and 1.6)%, respectively. The experimental data was correlated to an empirical equation, the form of which was decided by stepwise fit method. The average absolute percentage deviations between the data points and the equation were (0.23 and 0.10)% for R245fa and R236fa.     

新型PVT性质测试系统的研制

研制了一套新型压力-温度-体积（PVT）性质测试系统．该系统由自行开发的测控软件实时测控,温度测量精度可达±10mK,压力测量系统最大不确定度为±1．2KPa．利用新的测试系统对294～351K温度区间的Hydrofluorocarbons（HFC）-245fa饱和蒸气压进行了研究．实验结果表明,HFC-245fa的测量值与公认文献值的平均偏差小于0．03％,最大偏差小于0．484％,结果与文献值吻合较好．     

Surface tension of pentafluoroethane + 1,1-difluoroethane from (243 to 328) K

The surface tension of the binary refrigerant mixture pentafluoroethane (HFC-125) + 1,1-difluoroethane (HFC-152a) was measured in the temperature range from (243 to 328) K with a differential capillary rise method, for three compositions around the composition of the optimum refrigeration performance (HFC-125 + HFC152a, 15%/85%). The uncertainties of the measurement of the temperature and the surface tension were estimated to be within ±10 mK and ±0.2 mN m⁻¹, respectively. A correlation for the surface tension of the binary refrigerant mixture HFC-152a + HFC-125 was developed as a function of the composition.     

Dielectric properties of 1,1,1-trifluoroethane (HFC-143a) in the liquid phase

The relative permittivity (?_r) data of 1,1,1-trifluoroethane (HFC-143a), (CAS N# 420-46-2), a hydrofluorocarbon (HFC) developed as a refrigerant that has zero ozone depletion potential, is reported. The relative permittivity of HFC-143a in the liquid phase was measured using a direct capacitance method at temperatures from T = 218 to 294 K and at pressures up to P = 15 MPa, for a frequency of 10 kHz. The uncertainty of the ?_r measurements is estimated to be better than ±1.2 × 10⁻². A complete set of tables of experimental data as a function of temperature, pressure and density, is presented that covers the dielectric property needs for most engineering applications. To study the dependence of ?_r on density and temperature on a molecular basis, the theory developed by Vedam et al. and adapted by Diguet was applied to analyse the data. The Kirkwood modification of the Onsager equation was used to obtain the value of its dipole moment in the liquid phase (μ*). The apparent dipole moment obtained was μ* = 3.293 D. The effective dipole in the liquid state predicted by the Kirkwood–Frölich theory is 2.530 D. The measured values are compared with density functional and density functional self-consistent calculations (SCIPCM) of the electronic distribution and of the dipole moment of HFC-143a. Finally, the values of the isobaric thermal expansion and isothermal compressibility were estimated from the reported measurements.     

Isothermal vapor–liquid equilibrium data for the binary mixture difluoromethane (HFC-32) + ethyl fluoride (HFC-161) over a temperature range from 253.15 K to 303.15 K

Isothermal vapor–liquid equilibrium data of difluoromethane (HFC-32) + ethyl fluoride (HFC-161) mixture in the range of temperatures from 253.15 K to 303.15 K have been measured in the wide range of compositions. The experimental method used for this work is the single-cycle type. Using Peng–Robinson (PR) equation of state, combined with the first Modified Huron-Vidal (MHV1) mixing rule and Wilson model, the vapor–liquid equilibrium data are correlated. The correlation results have a good agreement with the experiment results. The average absolute vapor composition deviation is within 0.0125, and its largest absolute deviation of the vapor composition is 0.0568; the average relative pressure deviation is within 0.76% and its largest relative pressure deviation is 2.87%. In addition, the results reveal that there is no azeotrope in the binary system, and their temperature glides are small.     

Burning velocity measurement of HFC-41, HFC-152, and HFC-161 by the spherical-vessel method

The burning velocities of fluoromethane (HFC-41), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161) and ethane were measured by the spherical-vessel (SV) method at room temperature and at initial pressures of 80-107 kPa over a wide range of HFC/air equivalence ratios (?). The burning velocities were determined from the measured pressure increases by application of a spherical flame model. Schlieren photography was used to directly observe flame propagation behavior in a cylindrical vessel equipped with optical windows. The time evolution of the flame radii derived from the pressure increases agreed with the time evolution observed with the Schlieren technique. The maximum burning velocities of HFC-41, HFC-152, HFC-161 and ethane were 28.3 cm s⁻¹ at ? = 1.01, 30.1 cm s⁻¹ at ? = 1.07, 38.3 cm s⁻¹ at ? = 1.07 and 40.9 cm s⁻¹ at ? = 1.05, respectively. The maximum burning velocities for the HFCs, including previously reported C₁ and C₂ fluoroalkanes, decreased with increasing F-substitution rate (the ratio of the number of F atoms to the sum of the number of H and F atoms). The concentrations of chemical species in the flames were investigated by means of an equilibrium calculation, and the results suggested that the burning velocity was correlated with the concentrations of H and OH radicals that were not deactivated by F radicals in the flame. The results also suggested that the burning velocities were linearly related to the heats of combustion of the C₁ and C₂ fluoroalkanes.     

Vapor–liquid equilibria of the 1,1,1-trifluoroethane (HFC-143a) + dimethyl ether (DME) system

Binary vapor liquid equilibrium data were measured for the 1,1,1-trifluoroethane (HFC-143a) + dimethyl ether (DME) system at temperatures from 313.15 K to 363.15 K. These experiments were carried out with a circulating-type apparatus with on-line gas chromatograph analysis. The experimental data were correlated well by the Peng-Robinson equation of state using the Wong-Sandler mixing rules.     

Vapor pressures and PVT properties of 1,1,1,3,3-pentafluoropropane (HFC-245fa)

The vapor pressures and PVT properties of superheated vapor and compressed liquid of 1,1,1,3,3-pentafluoropropane (HFC-245fa) were measured at wide range of temperature and pressure. The simple correlation for vapor pressures, compressibility factors of superheated vapor and specific volumes of liquid were developed on the basis of the present measurements. The critical pressure was calculated by extrapolating the developed vapor pressure equation to the critical temperature. Isothermal compressibility of liquid was calculated from the developed Tait equation. Specific volume data obtained show the good linearity in the Hudleston plots. Overall uncertainty in the vapor pressure, compressibility factor and specific volume measurements is estimated less than ±5 kPa, ±1.2% and ±0.09%, respectively.     

(Vapour + liquid) equilibria of the {pentafluoroethane (HFC-125) + dimethyl ether (DME)} system

Binary (vapour + liquid) equilibrium data were measured for the {pentafluoroethane (HFC-125) + dimethyl ether (DME)} system at temperatures from (313.15 to 363.15) K. These experiments were carried out with a circulating-type apparatus with on-line gas chromatography. The experimental data were correlated well by the Peng-Robinson Stryjek-Vera equation of state using the Wong-Sandler mixing rules.     

Isothermal vapor–liquid equilibrium data for the binary mixture ethyl fluoride (HFC-161) + 1,1,1,2,3,3,3-heptafluoroproane (HFC-227ea) over a temperature range from 253.15 K to 313.15 K

Vapor–liquid equilibrium (VLE) data for the refrigerant mixture ethyl fluoride (HFC-161) + 1,1,1,2,3,3,3-heptafluoroproane (HFC-227ea) are reported in the temperature range from 253.15 K to 313.15 K with a single-phase circulation vapor–liquid equilibrium still. The results of the correlation for the vapor–liquid equilibrium data with Peng–Robinson (PR) equation of state (EOS), combined with the first Modified Huron-Vidal (MHV1) mixing rule and Wilson model, are presented. These results are in a good agreement with experimental data. The average and maximum derivations of vapor molar composition are within 0.0130 and 0.0295 respectively, and the average and maximum relative derivations of pressure are within 1.04% and 2.96%, respectively. The model parameters, determined from these binary data, are given to predict the phase behavior for a later ternary system. The binary system HFC-161 + HFC-227ea is a non-azeotropic mixture and exhibits a negative deviation from Raoult's law.     

An experimental investigation and modelling of the solubility, density and surface tension of 1,1,1,3,3-pentafluoropropane (R-245fa)/synthetic polyolester compressor oil solutions

This paper reports experimental data for the solubility, density and capillary constant for solutions of refrigerant 1,1,1,3,3-pentafluoropropane (R-245fa) with polyolester compressor oil Planetelf ACD 100FY over a wide range of temperatures and concentrations. The experimental data were obtained in the temperature range from 333 to 425 K and at pressures up to 33 bar using static methods. Based on information for the capillary constant, the surface tension of the solutions R-245fa/Planetelf ACD 100FY is determined. The enthalpy of liquid phase of the R-245fa/Planetelf ACD 100FY solutions is calculated. The analysis of the behaviour of the excess thermodynamic functions is carried out. Information about the changing concentration of refrigerant in the liquid phase of the refrigerant/oil solutions (ROS) and in the surface layer of the liquid phase of the ROS at increasing temperature is presented.     

Experimental studies on a mixture of HFC-32/125/161 as an alternative refrigerant to HCFC-22 in the presence of polyol ester

In this work, experiment was conducted to examine the thermo-physical properties of an alternative refrigerant to HCFC-22 in the presence of polyol ester (POE). The new alternative refrigerant is a mixture of HFC-32/125/161, whose physical properties are similar to HCFC-22 but has a lower global warming potential (GWP) than that of R407C. POE is used as the tested lubricating oil in the experiment. The saturated vapor pressure data and vapor–liquid equilibrium data of nine different mass fractions of the new refrigerant and polyol ester (POE) in the temperature range of 253–323 K were measured by single-phase cycle method. The experiment results showed that there was no stratification, no sediment generation in the liquid phase of the mixture, and the color of liquid phase of the mixture had no change in the equilibrium cell before and after the experiment with the POE concentration greater than 20% and the temperature higher than 258 K; with POE concentration lower than 20% and temperature lower than 258 K, stratification began to appear. Meanwhile, when POE and the refrigerant were miscible, the saturated pressure data of the mixture (HFC-32/125/161 + POE) revealed that POE had a very small impact on saturated vapor pressure of the mixture (almost negligible) when POE was less than 10% of the mixture; POE has an obvious effect on the saturated vapor pressure of the mixture when there is more than 10% POE in the mixture, especially when the temperature is higher than 283.15 K. Experimental data were correlated by Flory–Huggins model, Heil model, NRTL model and Wilson model. The results showed that to the average and maximum pressure deviation, the results were better with considering the effects of temperature on the energy parameters. Among the above models, the NRTL activity coefficient model was the best, the Heil and Wilson models followed and the Flory–Huggins model had the largest deviation from the experimental data.     

A facile synthetic method for 2-fluoroindolizines from 1-chloro-2,2,2-trifluoroethane (HCFC-133a) and 1,1,1,2-tetrafluoroethane (HFC-134a)

In the presence of KOH and Et₃N, pyridinium and isoquinolinium N-ylides generated in situ from their bromides react with 1-chloro-2,2,2-trifluoroethane (HCFC-133a, bp 6 °C) or 1,1,1,2-tetrafluoroethane (HFC-134a, bp −27 °C) to give the corresponding 2-fluoroindolizines via 1,3-dipolar [3+2] cycloaddition at 80-100 °C in DMSO at atmospheric pressure in normal glassware.     

PVTx measurements in the gas phase for binary mixtures of HFC-161 and HFC-227ea

The gaseous PVTx properties of ethyl fluoride (HFC-161) + 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) mixtures were measured at temperatures from 318.180 to 403.205 K and corresponding pressures from 961.3 to 3129.8 kPa using the isochoric method. The uncertainties in the present measurements were estimated to be ±1.5 kPa for pressure and ±6 mK for temperature. On the basis of the experimental PVTx property data, a truncated virial equation of state was developed for the binary HFC-161/227ea system. This equation reproduced the experimental data in the gas phase within ±0.164% in pressure and within ±0.178% in density.     

Rate coefficients for the reactions of OH with CF3CH2CH3 (HFC-263fb), CF3CHFCH2F (HFC-245eb), and CHF2CHFCHF2 (HFC-245ea) between 238 and 375 K

Rate coefficients for reaction of the hydroxyl radical (OH) with three hydrofluorocarbons (HFCs) CF3CH2CH3, HFC-263fb, (k1); CF3CHFCH2F, HFC-245eb, (k2); and CHF2CHFCHF2, HFC-245ea, (k3); which are suggested as potential substitutes to chlorofluorocarbons (CFCs), were measured using pulsed laser photolysis-laser-induced fluorescence (PLP-LIF) between 235 and 375 K. The Arrhenius expressions obtained are k1(T) = (4.36 +/- 0.72) x 10(-12) exp[-(1290 +/- 40)/T] cm3 molecule(-1) s(-1); k2(T) = (1.23 +/- 0.18) x 10(-12) exp[-(1250 +/- 40)/T] cm3 molecule(-1) s(-1); k3(T) = (1.91 +/- 0.42) x 10(-12) exp[-(1375 +/- 100)/T] cm3 molecule(-1) s(-1). The quoted uncertainties are 95% confidence limits and include estimated systematic errors. The present results are discussed and compared with rate coefficients available in the literature. Our results are also compared with those calculated using structure activity relationships (SAR) for fluorinated compounds. The IR absorption cross-sections at room temperature for these compounds were measured over the range of 500 to 4000 cm-1. The global warming potentials (GWPs) of CF3CH2CH3(HFC-263fb), CF3CHFCH2F(HFC-245eb), and CHF2CHFCHF2(HFC-245ea) were calculated to be 234, 962, and 723 for a 20-year horizon; 70, 286, and 215 for a 100-year horizon; and 22, 89, and 68 for a 500-year horizon; and the atmospheric lifetimes of these compounds are 0.8, 2.5, and 2.6 years, respectively. It is concluded that these compounds are acceptable substitutes for CFCs in terms of their impact on Earth's climate.     

New hydrofluorocarbon (HFC) solvents for antimony pentafluoride: Generation and characterization of 1-alkoxypentafluoroallyl cations

Certain hydrofluorocarbons (HFC) stable towards the strong Lewis acid, antimony pentafluoride, were found to function as a solvent for this aggressive reagent. CF₃CF₂CH₂F (HFC-236cb) was demonstrated to be an excellent solvent for SbF₅ and was used for the generation of stable polyfluorinated benzyl and allyl cations. Using this solvent 1-methoxypentafluoroallyl cation and R_FOCFCFCF₂⁺ (R_F = n-C₃F₇ and n-C₄F₉), were generated and characterized by NMR spectroscopy.     

Isothermal phase equilibria for the (HFC-32 + HFC-134a) mixed-gas hydrate system

Isothermal phase equilibria (pressure-composition relations in hydrate, gas, and aqueous phases) in the {difluoromethane (HFC-32) + 1,1,1,2-tetrafluoroethane (HFC-134a)} mixed-gas hydrate system were measured at the temperatures 274.15 K, 279.15 K, and 283.15 K. The heterogeneous azeotropic-like behaviour derived from the structural phase transition of (HFC-32 + HFC-134a) mixed-gas hydrates appears over the whole temperature range of the present study. In addition to the heterogeneous azeotropic-like behaviour, the isothermal phase equilibrium curves of the (HFC-32 + HFC-134a) mixed-gas hydrate system exhibit the negative homogeneous azeotropic-like behaviour at temperatures 279.15 K and 283.15 K. The negative azeotropic-like behaviour, which becomes more remarkable at higher temperatures, results in the lower equilibrium pressure of (HFC-32 + HFC-134a) mixed-gas hydrates than those of both simple HFC-32 and HFC-134a hydrates. Although the HFC-134a molecule forms the simple structure-II hydrate at the temperatures, the present findings reveal that HFC-134a molecules occupy a part of the large cages of the structure-I mixed-gas hydrate.     

Burning velocity measurements of fluoropropanes by the spherical-vessel method

Burning velocity measurements of six types of fluoropropanes including structural isomers were carried out in order to understand the flammability of hydrofluorocarbons (HFC). The burning velocity (S_u) was determined by applying a spherical flame model to the pressure rise during combustion, which was measured at room temperature and at initial pressures of 80-107 kPa over a wide range of HFC/air concentrations. The maximum S_u of 1-fluoropropane (HFC-281fa), 2-fluoropropane (HFC-281ea), 1,3-difluoropropane (HFC-272fa), 2,2-difluoropropane (HFC-272ca), 1,2,3-trifluoropropane (HFC-263ea), and 1,1,1-trifluoropropane (HFC-263fb) was 35.0, 31.8, 31.9, 21.2, 25.7, and 14.5 cm s⁻¹, respectively. Note that the maximum S_u of HFC-263ea was appreciably higher than that of HFC-272ca, which shows the importance of the F-atom distribution, as well as of the F/H ratio in the HFC molecule. The results of equilibrium calculation for these HFCs showed that S_u is positively correlated with the flame temperature and the concentrations of the active chain carriers H and OH in the flame. We conducted a trial to interpret the magnitude of S_u by means of the effects of substituents for C₁-C₃ HFCs. As a result, it has been found that the order of inhibition efficiency for S_u decreases in the order of CF₃ > CF₂ > CF.     

Adsorptive removal of halo-olefinic impurities from 1,1,1,3,3-pentafluoropropane over ion-exchanged Y zeolites

Various metal cations exchanged Y zeolites were prepared via the exchange of NaY zeolite with aqueous solutions containing K⁺, Ca²⁺, Cu²⁺, La³⁺ and Ce³⁺ cations, respectively. The influence of the extra-framework cations nature of these ion-exchanged Y zeolites on their adsorption performance for a low content of halo-olefinic impurities, mainly including 1-chloro-3,3,3-trifluoro-1-propene (HCFC-1233zd), 1-chloro-1,3,3,3-tetrafluoro-1-propene (HFC-1224zb) and 2-chloro-1,3,3,3-tetrafluoro-1-propene (HFC-1224xe), in the 1,1,1,3,3-pentafluoropropane (HFC-245fa) product after distillation was investigated. HCFC-1233zd impurity can be substantially removed from HFC-245fa product feed via the adsorption over multivalent metal cations and Cu⁺ cation exchanged Y zeolites, which is ascribed to the formation of π-adsorption complexes between HCFC-1233zd and zeolites, rather than over alkaline metal cations exchanged Y zeolites. Among multivalent metal cations exchanged Y zeolites, CeY has the highest adsorption capacity for HCFC-1233zd and best regeneration performance, due to its lowest density of strong Brønsted and weak Lewis acid sites as well as high framework stability during the regeneration. Regardless of the cations introduced in Y zeolite used as an adsorbent, HCFC-1224zb and HCFC-1224xe impurities are not obviously removed from HFC-245fa product feed via the adsorption, maybe due to more halogen atoms linked with the double bond in them comparing with HCFC-1233zd.