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J.

of Supercritical Fluids 41 (2007) 217226

PVT measurements for pure methanol in the near-critical and supercritical regions
A.R. Bazaev, I.M. Abdulagatov , E.A. Bazaev, A.A. Abdurashidova, A.E. Ramazanova
Institute for Geothermal Problems of the Dagestan Scientic Center of the Russian Academy of Sciences, 367030 Makhachkala, Shamilya Str. 39, Dagestan, Russia Received 23 May 2006; received in revised form 22 September 2006; accepted 23 September 2006

Abstract PVT properties of pure methanol were measured in the near-critical and supercritical regions. Measurements were made with a constant-volume piezometer immersed in a precision air thermostat. The maximum uncertainty of the density measurements was estimated to be 0.15%. The uncertainties of the temperature and pressure measurements were, respectively, 15 mK and 0.05%. Measurements were performed at seven nearcritical isochores between 113 and 370 kg m3 and at pressures from 1.4 to 40 MPa. The range of temperature was 423653 K. Using the two-phase PVT data, the values of vaporpressure and saturated liquid and vapor density were determined by means the analytical extrapolating technique in the temperature range from 423 to 512.7 K. The measured one-phase PVT data and saturated property data (TS , PS , S , S ) for pure methanol were compared with the values calculated from fundamental IUPAC and crossover equations of state and with precise experimental PVT data reported by other authors. From the saturated liquid and vapor density and vaporpressure data in the critical region the values of the critical parameters (TC = 512.75 0.1 K, PC = 8.120 0.02 MPa, and C = 271.6 3 kg m3 ) were extracted. For three isochores (113.5, 252.4, and 368.2 kg m3 ) the measurements were performed in both cooling and heating regimes to estimate the effect of thermal decomposition (chemical reaction) on the PVT properties of methanol. 2006 Elsevier B.V. All rights reserved.
Keywords: Critical point; Coexistence curve; Equation of state; Methanol; Saturated density; Vaporpressure

1. Introduction The possibility of the chemical reactions occurring during thermophysical properties measurements for methanol was reported in series works [17]. Difculty to exact measurements of thermodynamic properties of methanol at high temperatures is that at temperatures above 405 K methanol begins to decompose [1,2]. Some authors claimed that the decomposition of the methanol taking place at temperatures above 423 K [5] or 473 K [6]. Probably this is depending on measuring properties and sensitivity of the method of measurement on the results of chemical reaction and depends on materials of the measuring cell. In PVT experiments when the methanol is conned in the piezometer at temperature above 405 K for several hours the decomposi-

Corresponding author. Present address: Physical and Chemical Properties Division, National Institute of Standards and Technology, 325 Broadway, Boulder, CO 80305, USA. Tel.: +1 303 497 4027; fax: +1 303 497 5224. E-mail address: ilmutdin@boulder.nist.gov (I.M. Abdulagatov).

tion of the methanol molecules may cause signicant effect on measured values of pressure. Little is known about the effect of decomposition on the thermodynamic properties of methanol. The decomposition products depend on the metals and metallic oxides in contact with the vapor [3,6,8]. Measurements at high temperatures for methanol by Straty et al. [2] and by Taani [3] found the decomposition effect on PVT measurements. Analysis of the methanol sample after experiments showed the presence of hydrogen, carbon monoxide, carbon dioxide, formaldehyde, methyl formate, and dimethyl ether [1,6]. The presence of the gases in the liquid methanol after measurements have been found in the calorimetric experiments [4,5,7] also. Residual pressure due to presence gaseous phase after measurements in the calorimeter (before open the calorimeter was cooled with liquid nitrogen) was noted [4,5,7]. The magnitude of the decomposition effect depends on temperature and residence time in the piezometer. Bruno and Hume [9] described several experimental approaches for dealing with chemical reactions or decomposition which can occur when making thermophysical property measurements at high temperatures and high pressure.

0896-8446/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.supu.2006.09.012

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Methanol is a small and highly polar molecule, and my be expected to interact strongly with other uid in a H-bonded network [10]. Therefore, in mixtures in which methanol one of the component, the thermodynamic properties exhibit some anomaly [1114]. Raman spectroscopic studies on H-bonding in methanol under high temperature and pressure were study by Ebukuro et al. [15]. They found that weak hydrogen bonding remains even at the critical temperature. Thermodynamic properties of strongly associated uids such as methanol provide insight to our understanding of the effect of H-bonding on its behavior. There are other theoretical problems connected with the behavior H-bond in the supercritical conditions and structure of the associated uids in the supercritical conditions. The experimental studying of the PVT behavior of the near-critical and supercritical methanol can be serving as an example for other strongly associated uid such as water (more convenient T and P range and easier for measurements by avoiding severe supercritical water conditions). Methanol is important industrial chemical material also. Methanol is one of the main additives used in natural gas processing and pipeline transport and used as a hydrate inhibitor and as secant following hydraulic tests of natural gas pipelines [16]. Often methanol is found with water in natural gases. Increasing Mobil Corp.s methanol to gasoline conversion process. In 1980, world demand for methanol about 12 106 tonnes. Today this is increased up to 50 106 tonnes. Methanol is very important uid as a fuel and feedstock and interest in view of its connection with coal, natural gas and biomass gasication; various applications such as: transport and storage of hydrogen, natural refrigerants, and working uids in new power cycles. Methanol also used as a polar modier to enhance the solubility of certain solutes by several orders of magnitude [1719]. Adding of a small amount of methanol (cosolvent) can have dramatically effect on supercritical uid phase behavior [20]. A survey of the literature reveals that measurements of the thermodynamic properties of pure methanol in the near-critical and the supercritical regions (TC = 512.6 K, PC = 8.1035 MPa, and C = 275.56 kg m3 ) are very scarce. Only four data sets [2,3,21,22] were found for PVT measurements of methanol in the supercritical region. Three of them [2,21,22] were performed of the measurements at temperatures up to 573 K with uncertainty of 0.20.3%. The data by Taani [3] cover the temperature range up to 623 K. IUPAC fundamental equations of state [23] is represents the thermodynamic properties of methanol in the temperature range from 175.61 to 620 K at pressures up to 800 MPa. The uncertainty of the calculated values of density is 0.1%. Therefore, all previous reported experimental PVT data for methanol are covering the temperature range up to 620 K with accuracy of 0.20.3%. There are very few PVT and saturated density measurements in the immediate vicinity of the critical point to accurate determine the values of the critical parameters. This is one of the reasons why available experimental critical parameters data and saturated densities in the critical region for methanol show large discrepancy. For example, all available critical temperatures of methanol lied between 512.2 and 513.8 K, while the scattering in saturated densities is within 1315 kg m3 . Therefore, the main objective of the present paper is to provide new

accurate (with uncertainty of 0.120.15%) experimental PVT, saturated (PS , S , TS ) and critical (TC , PC , C ) properties data for pure methanol in the near-critical and supercritical regions and to extend available measured data up to 653 K. Therefore, the present results considerably expand the temperature range and database in which PVT for methanol is available. The present results can be used also in future to improve the accuracy and extent the range of applicability of the IUPAC formulation [23] of the equation of state and to develop accurate crossover model for methanol in the critical region. We also proved comprehensive analysis of the available experimental PVT, saturated and critical properties data for pure methanol to estimate the reliability and consistency of the published datasets. The effect of thermal decomposition on the measured values of PVT for the methanol is studied. This work is a part of a continuing program on the volumetric (PVT) and caloric (CV VT) properties measurements of alcohols and their aqueous solutions in the critical and supercritical regions. 2. Experimental 2.1. Experimental apparatus and method The details of the high-temperature and high-pressure PVT apparatus and procedures used for the present measurements have been described in our previous publications [2438] and were used without modication. Only essential information will be given here. The measurements were made using the constant-volume method, with an extraction of the sample from the piezometer under isothermal conditions. The high-pressure piezometer is constructed of heat and corrosion resistant high-strength alloy EI-43BU-VD (nickel, 77.00%; chrom, 19.84%; titanium, 2.82%; aluminium, 0.8%; iron, 0.59%; silicon, 0.44%; copper, 0.01%). The inner volume of the piezometer was calculated by taking into consideration the corrections of the elastic pressure deformation and thermal expansion. The internal volume of the piezometer was calibrated by lling it with pure water and then withdrawing the water in small amounts and weighing them. The weight of the water withdrawn m(H2 O) yielded the volume of the piezometer VT0 P0 = m(H2 O)/(H2 O) from the well established density (H2 O) of water at temperature T0 and pressure P0 of the calibration. The reference value for the density of water (H2 O) = 762.22 kg m3 was taken from the well-established PVT information (IAPWS formulation, Wagner and Pru [39]) at a temperature of T0 = 673.15 K and a pressure of P0 = 38.35 MPa. The volume of the piezometer at these conditions was VP0 T0 = 32.56 0.014 cm3 . All masses were determined with an uncertainty of 5 104 g. This calibration was checked using other pure uids (carbon dioxide, for example). The resulting value of the piezometer volume was essentially the same as determined with water (difference is about 0.03%). The volume of the piezometer at any other given temperature T and pressure P was measured with an uncertainty of 0.040.05%. It is necessary to know the volume of the piezometer, VPT , at given temperature T and pressure P, for the purpose of calculating densities (T, P) = m/VPT . Variations of the piezometer volume VPT with temperature T and pressure P

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were calculated with the equation VPT = VP0 T0 [1 + 3(T T0 ) + (P P0 ], (1)

where = 1.56 105 K1 is the thermal expansion coefcient of piezometer material, which is almost independent of temperature in the range from 400 to 700 K and = 3.51 105 MPa1 is the pressure expansion coefcient of the piezometer. The uid under study was thermostated in a double-wall air bath with an inside volume of 65 dm3 . To minimize temperature gradients in the thermostat, two electrically driven high-speed fans were used. The temperature inside the thermostat was maintained uniform within 5 mK with the aid of guard heaters located between the thermostat walls and regulating heaters, which were mounted inside the thermostat. The temperature inside the thermostat and the uid temperature were controlled automatically [40]. To reach equilibrium quickly, the electric heater was switched on and the sample was stirred with a steel ball bearing, which was rotated rapidly in the sample by a mechanical oscillation of the piezometer around the horizontal axis. The uid temperature was measured with a 10 platinum resistance thermometer (PRT-10). The PRT was calibrated by VNIIFTRI (Moscow) on ITS-90. The maximum uncertainty in the measured temperature was 15 mK. In order to avoid the additional uncertainty in the density measurements which introduced by the noxious volume, a diaphragm-type null indicator was mounted on one of the ends of the piezometer. The diaphragm (40 mm in diameter and 0.05 mm thick) was made from 321 stainless steel. The diaphragm-type null indicator was connected with a dead-weight pressure gauge MP-600 by a stainless steel tube lled with liquid n-octane. The membrane was compressed between the piezometer body and null-indicator body with bolts. The average uncertainty in pressure measurements was 0.02%, and the maximum uncertainty was 0.05%. Taking into account the uncertainties of measurements of temperature and pressure, the total experimental uncertainty of density was estimated to be 0.120.15% in the critical region. In order to check the reproducibility of the experimental values, some of the measurements at selected temperature and pressure were repeated at different times. The reproducibility of the data corresponding to repeated (P, T) is better than 0.1%. To check and conrm the accuracy of the measurements, PVT measurements were made on the pure water. The measured values of density and pressure for two selected supercritical isotherms, 643.15 and 653.15 K, of pure water were compared with the values calculated from the IAPWS formulation [39]. The absolute average deviation (AAD) in the critical region is within 0.200.35%. This agreement conrms the reliability and accuracy of the present PVT data for the pure methanol. 2.2. Procedure of the measurements Pressure of the methanol was measured as a function of temperature at nearly constant density. The piezometer was lled at room temperature, sealed off, and heated along the quasiisochore. Each run for the PVT measurements was normally started at low temperatures (at 423.15 K) in the two-phase region

or in the vapor phase and completed in the one-phase (liquid or vapor depending on lling factor) region at its highest temperature or pressure. After reached the desired temperature (423.15 K) the sample was maintained in the piezometer for 23 h. After thermal equilibration (P, V, T,) measurements along quasi-isochore were made, starting from the minimal temperature of 423.15 K. Just after reached the desired temperature the sample pressure was recorded as a function of time. At low temperatures (below 573 K) the thermal equilibrium was reached for the short time (11.5 h). But, starting with the temperature of 573 K we found that the pressure essentially changed with time. The rate of pressure changes depend on experimental temperature and density (increase with density). The rate of pressure changes is varied in the range of 0.40.8 Pa per sec for isochore of 368.2 kg m3 for temperatures between 573 and 653 K. After 23 h the pressure in the piezometer at given temperature and density is stabilized. The stabilized values of the pressure was xed as nal experimental values of pressure corresponding for the given temperature and density. Therefore, the measured values of PVT for methanol in this work are the results of the measurements of the pressure in the piezometer after 23 h stabilization due to thermal decomposition effect on the measured values of pressure. After reached maximum measured temperature 653 K, the sample was cooled (cooling run) up to initial temperature (423 K) and measured the pressure at approximately the same temperatures as in heating run in order to compare with the results in heating run. After measurements the sample (isochore 368.2 kg m3 ) was analyzed by using the chromatograph (Chrom-5) to check the components of the thermal decomposition. Analysis of the liquid phase showed the presence of 5.16 wt% of formaldehyde (HCOH) and 1.19 wt% dimethyl ether (CH3 OCH3 ) and some gases which were not identied. After complete the measurement for given isochore the piezometer was discharged and new sample was used to continue the measurements for the other isochores. The commercial supplier of the methanol provided a purity analysis of 99.93 mole%. 3. Results and discussion Measurements of the PVT relationships for pure methanol were performed along seven near-critical isochores, namely: 113.5, 138.6, 177.6, 252.4, 305.2, 360.5, and 368.2 kg m3 . The temperature ranged between 423 and 653 K and the pressure ranged from 1.4 to 40 MPa. The experimental results of temperature, density, and pressure measurements in the heating and cooling runs for the near-critical and supercritical methanol are presented in Table 1 (run-1, heating and run-2, cooling) and shown in Figs. 13. The vaporpressure data extracted from these two-phase PVT measurements are presented in Table 2. The saturated liquid and vapor densities for nine temperatures between 423 and 503 K, were derived by extrapolation of measured two-phase PVT data to the saturation pressure (by using the vaporpressure equation of Ambrose and Walton [41]). The values of the saturated properties (saturated temperatures and vaporpressures) for four measured isochores (113.5, 252.4, 360.5, and 368.2 kg m3 ) were also derived by using the iso-

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Table 1 Experimental values of the PVT properties of pure methanol along the near-critical and supercritical isotherms T (K) Density, (kg m3 ) 113.5 Run-1, heating 423.15 433.15 443.15 453.15 463.15 473.15 483.15 493.15 503.15 513.15 523.15 533.15 543.15 553.15 563.15 573.15 583.15 593.15 603.15 613.15 623.15 633.15 643.15 653.15 Run-2, cooling 423.15 433.15 443.15 453.15 463.15 473.15 483.15 493.15 503.15 513.15 523.15 533.15 543.15 553.15 563.15 573.15 583.15 593.15 603.15 613.15 623.15 633.15 643.15 653.15 Values are P (MPa). 1.400 1.760 2.201 2.706 3.307 4.024 4.845 5.803 6.900 7.341 8.089 8.693 9.311 9.943 10.588 11.248 11.921 12.609 13.310 14.026 14.755 15.498 16.255 17.026 2.254 2.641 3.129 3.701 4.336 5.017 5.724 6.438 7.139 7.800 8.551 9.156 9.769 10.390 11.018 11.655 12.300 12.953 13.613 14.282 14.959 15.643 16.336 17.036 138.6 7.859 8.619 9.390 10.174 10.969 11.776 12.595 13.426 14.269 15.123 15.990 16.868 17.758 18.661 19.575 177.6 8.134 9.114 10.105 11.105 12.115 13.135 14.164 15.204 16.253 17.312 18.381 19.460 20.549 21.647 22.755 252.4 1.401 1.761 2.201 2.708 3.309 4.029 4.852 5.805 6.912 8.199 9.567 10.944 12.329 13.722 15.124 16.533 17.950 19.375 20.808 22.250 23.699 25.157 26.622 28.096 2.059 2.426 2.854 3.359 3.953 4.653 5.472 6.425 7.527 8.790 10.155 11.521 12.890 14.262 15.636 17.012 18.390 19.771 21.154 22.539 23.926 25.316 26.709 28.103 305.2 8.195 9.879 11.571 13.269 14.975 16.688 18.408 20.135 21.869 23.610 25.359 27.114 28.877 30.647 32.424 360.5 1.398 1.762 2.203 2.705 3.316 4.025 4.847 5.801 6.899 8.196 10.190 12.334 14.489 16.654 18.828 21.013 23.207 25.412 27.626 29.851 32.085 34.329 36.584 38.848 368.2 1.399 1.760 2.204 2.706 3.315 4.026 4.853 5.803 6.905 8.221 10.274 12.444 14.609 16.850 19.047 21.580 23.829 26.093 28.374 30.671 32.983 35.311 37.655 40.016 1.852 2.289 2.730 3.209 3.759 4.415 5.211 6.182 7.362 9.000 10.958 13.110 15.276 17.456 19.650 21.858 24.080 26.316 28.566 30.830 33.108 35.400 37.706 40.026

choric and isothermal break-point techniques (see Fig. 4). The results are presented in Table 2. Figs. 13 also contain the results of PVT calculated with IUPAC fundamental equation of state [23], Goodwin equation of state [42], and crossover model by Abdulagatov et al. [5]. Fig. 1 demonstrate the measured values of pressure P as a function of density along the seven supercritical isotherms together with

the data reported by other authors and the values calculated with IUPAC equation of state [23]. Fig. 2 represent the values of PVT measured in the near sub-critical (two-phase region) and in the near supercritical regions together with values calculated from IUPAC [23] and crossover equation [5] of states. The experimental and calculated values of compressibility factor Z = PV/RT as a function of pressure P are given in Fig. 3. This gure contains

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Fig. 1. Measured pressures of the methanol as a function of density along the various supercritical isotherms together with data reported by other authors and values calculated with the IUPAC fundamental equation of state [23]. (1) 513.15 K; (2) 523.15 K; (3) 533.15 K; (4) 543.15 K; (5) 553.15 K; (6) 5 63.15 K; (7) 573.15 K. See Refs. [2,2123,52,53].

Fig. 3. Compressibility factors, Z = PV/RT, of the methanol as a function of pressure P along the supercritical isotherms together with data reported by other authors and values calculated with IUPAC [23] and Goodwin [42] nonanalytical equations of state. (1) 513.15 K; (2) 523.15 K; (3) 533.15 K; (4) 543.15 K; (5) 553.15 K; (6) 563.15 K; (7) 573.15 K. See Refs. [2123,42].

also the values of compressibility factor Z calculated and measured by other authors from the literature. Fig. 3 demonstrates good mutual consistency between measurements of temperature T, pressure P, and specic volume V for each thermodynamic state (P, V, T) and the results of calculation by IUPAC [23] and Goodwin [42] equations of state. As one can see from Figs. 13, there is general agreement (within 0.20.5%) among the various datasets and the values calculated with IUPAC [23] and Goodwin [42] equations of state. In the critical region, the deviation

between calculated and measured values of Z reached up to 2% and more. The derived values of vaporpressure and saturated liquid and vapor density are presented in Figs. 5 and 6 together with values reported by other authors and calculated from various correlations. The critical region of the coexistence curve is depicted in Fig. 6b together with calculated and reported data. Fig. 6a contains also the values of saturated density derived in calorimetric experiments [5,7] in the critical region in the present data together with IUPAC [23] calculations. As one can see from Fig. 6b, very few saturated density data are available for methanol in the critical region. The scattering various datasets and correlations for methanol in the critical region is within 1 K (for saturated temperature TS ) and within 15 kg m3 (for saturated density).
Table 2 Experimental values of the temperature (TS ), vaporpressure (PS ), liquid (S ) and vapor (S ) densities of methanol at saturation TS (K) 423.15 433.15 443.15 453.15 463.15 473.15 483.15 493.15 503.15 PS (MPa) 1.3995 1.7610 2.2023 2.7068 3.3120 4.0260 4.8490 5.8038 6.9055 TS (K) S (kg m3 ) 645.94 630.37 613.06 594.64 573.59 549.23 520.56 484.22 431.96 S (kg m3 ) 16.07 20.55 26.26 33.06 41.52 52.11 66.47 88.55 124.63 PS (MPa) 7.78 7.87 8.07 6.62

Fig. 2. Measured pressures of the methanol as a function of density along the various near sub-critical and near supercritical isotherms together with values calculated from IUPAC fundamental equation of state [23] and crossover model [5]. (1) 423.15 K; (2) 433.15 K; (3) 443.15 K; (4) 453.15 K; (5) 463.15 K; (6) 473.15 K; (7) 483.15 K; (8) 493.15 K; (9) 503.15 K; (10) 513.15 K; (11) 523.15 K; (12) 533.15 K; (13) 543.15 K; (14) 553.15 K; (15) 563.15 K. See Refs. [5,23].

S (kg m3 )

From isochoric break-point technique 368.2 510.41 360.5 510.93 252.4 512.70 113.5 500.78

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Fig. 4. Intercepts of the 368.2 and 113.5 kg m3 isochores with the vaporpressure curve for the methanol. () One-phase; ( ) two-phase; () vaporpressure point.

The measured values of saturated density were used to estimate the values of the critical parameters for pure methanol. Fig. 7a shows the density differences, = S S , at saturation as a function of temperature in the critical region. The values of = S S were analytically extrapolated to zero ( 0) by using the scaling relation for the saturated densities, to estimate the value of the critical temperature. The optimal values of the temperature (TC = 512.75 K), where 0, was accepted as the value of the critical temperature for pure methanol. Fig. 7b demonstrate the values of coexistence curve diameter, d = (L + V )/2, as a function of reduced temperature, = (T TC )/TC , where the critical temperature is TC = 512.75 0.2 K. In order to estimate the value of the critical density, C , of pure methanol from the saturated density data, the

values of the coexistence curve diameter d data were analytically extrapolated to zero reduced temperature ( 0) using the scaling relation for the diameter. The derived value of the critical density for pure methanol is C = 271.6 3 kg m3 . The present vaporpressure values as a function of reduced temperature are presented in Fig. 7c. The measured values of the vaporpressures were also analytically extrapolated to 0, using the scaling relation for the vaporpressure near the critical point, to estimate the value of the critical pressure. The derived value of the critical pressure is PC = 8.120 0.02 MPa. The derived values of the critical parameters for methanol (TC = 512.75 0.2 K, PC = 8.120 0.02 MPa, and C = 271.6 3 kg m3 ) are good agree with the values recommended by IUPAC [23] and Gude and Teja [43]. Differences in the critical temperature, pressure,

Fig. 5. Vaporpressures for the methanol reported by various authors together with the present data. See Refs. [2,23,42,4446,50,51,5461,6366].

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Fig. 6. Saturated liquid and vapor densities for the methanol reported by various authors together with the present results in the critical region. See Refs. [2,4,5,23,42,44,4749,50,53,58,59,62].

and density are within 0.15 K, 0.04 MPa, and 4 kg m3 ), respectively. In order to study the effect of thermal decomposition of methanol molecules on the measured values of pressure, the measurements for three isochores (113.5, 252.4, and 368.2 kg m3 ) were performed in heating and cooling runs. As

Table 1 shows the maximum difference in pressure between both heating and cooling runs are 61%, 47%, and 32% for 113.5, 252.4, and 368.2 kg m3 , respectively. The values of the pressure in the cooling runs are higher than in the heating runs due to enrichment of decomposition products, e.g. due to formation of gaseous products. After the measurements, gases thought to

Fig. 7. The present saturated density differences (a) temperature near the critical point.

= S S , coexistence curve diameter; (b) d = (L + V )/2, and (c) vaporpressures, PS , as a function of

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cal cal Fig. 8. Percentage deviations, PS = 100(PS PS /PS ) (left) and = 100(exp cal /exp ) (right) of the present experimental vaporpressures and saturated densities for the methanol from the values calculated with various correlations and IUPAC equation of state by other authors. See [21,23,41,42,4448,50].

exp

be decomposition products, were released from the piezometric cell. The effect of decomposition on measured pressures is starting in heating run at temperatures is about 573 K, therefore, at T > 573 K the difference between the measured pressures in cooling and heating runs is small (about 2.53.5%), while at low temperatures is about 4560%. The PVT data of methanol measured in this work were compared with the values reported by other authors. Detailed comparisons the present PVT data with various datasets and calculations with equations of state from the literature reveals that in general the agreement satisfactory. The differences between the present data and the values of density calculated with IUPAC equation of state [23] is good (AAD = 0.38%) in the temperature range above 593 K and densities above 260 kg m3 , while at low densities ( < 260 kg m3 ) and higher temperatures the deviations reached up to 56%. An acceptable agreement within 0.47% is found between the measured and calculated values of density at the low temperatures (T < 553 K) and low densities ( < 180 kg m3 ), while at high densities and low temperatures the deviations are reached up to 12%. Crossover model [5] were
Table 3 Deviation statistics for vaporpressure and saturated density data Deviation Vaporpressure data AAD Bias Standard deviation Standard error Maximum deviation N Deviation Saturated density data AAD Bias Standard deviation Standard error Maximum deviation N Skaates [46] 0.24 0.12 0.29 0.12 0.54 36 Goodwin [42] 0.18 0.18 0.24 0.09 0.69 9 Ambrose [41] 0.20 0.12 0.25 0.08 0.57 36 Kozlov [44] 0.90 0.90 0.30 0.11 1.04 9 Goodwin [42] 0.22 0.18 0.21 0.07 0.54 36 Zubarev [21] 0.50 0.41 0.33 0.11 0.87 9

found to reproduce the present PVT data for methanol with an AAD = 0.63%. Fig. 8 (left) represented the percentage deviations between the present vaporpressure data and the values calculated from the various correlations and IUPAC [23] equation of state from the literature. It can be seen that the deviations in vaporpressure are lower than 0.5%, except for the a few data points at low temperatures (this points are not included in Fig. 8), where differences reached up to 0.8%. The deviations of the vaporpressure data calculated from Ambrose and Walton [41] and Kozlov [44] correlations and the data reported by Zubarev and Bagdonas [21], de Loos [45], and Skaates and Kay [46] were less than 0.3%. Good agreement within 0.22% (maximum deviation is 0.52%) is found between the present vaporpressure data and the values calculated with IUPAC EOS [23]. Crossover model [5] calculations differ from the present vaporpressure data with an AAD = 0.12%. Fig. 8 (right) represent the deviations between the present saturated densities for methanol and the values calculated from the various correlations and IUPAC [23] equation of state by other authors. An excellent agreement within 0.06%

Kozlov [44] 0.21 0.12 0.21 0.07 0.46 36 IUPAC [23] 0.06 0.03 0.08 0.03 0.06 9

Zubarev [49] 0.39 0.39 0.23 0.08 1.02 36 Cibulka [47] 0.13 0.13 0.11 0.04 0.38 9

IUPAC [23] 0.22 0.13 0.23 0.04 0.52 36 Donham [51] 0.48 0.48 0.30 0.10 0.81 9

de Loos [45] 0.40 0.10 0.52 0.17 0.80 36 Hales [48] 0.24 0.24 0.24 0.08 0.71 9

Machado [50] 0.50 0.50 0.38 0.16 1.00 36 Machado [50] 0.23 0.23 0.07 0.03 0.34 9

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is found between the present data and the values of the saturated liquid density calculated with IUPAC [23], while the difference between saturated vapor densities were within 0.5% (AAD = 0.3%). The values of saturated liquid density calculated from the correlation by Cibulka [47] and the data reported by Hales and Ellender [48] differs from the present results by 0.1% at temperatures up to 480 K, while at temperatures close to the critical point the deviations increases up to 0.5%. Systematic positive deviations are about 0.30.5 % was found with the data of Zubarev and Bagdonas [21]. Differences are up to 0.93 % for the present saturated density data and crossover model [5]. The deviation statistics for the present results and the selected vaporpressure and saturated liquid density datasets and the values calculated with various correlations are presented in Table 3. 4. Conclusions By means of a constant-volume piezometer, PVT properties of pure methanol have been measured in a range of temperatures from 423 to 653 K, pressures from 1.4 to 40 MPa, and densities from 113.5 to 368.2 kg m3 with an estimated uncertainty of 0.15%. The vaporpressure data were measured for temperatures between 423 and 512.7 K. The measured data show good agreement (AAD = 0.22%, maximum deviation is 0.52%) with the values calculations from IUPAC fundamental equation of state. The values of saturated liquid and vapor densities for pure methanol in the temperature range from 423 to 512.7 K were derived from the two-phase PVT measurements using extrapolating technique. The derived saturated liquid and vapor densities were used to estimate the values of the critical parameters for pure methanol (TC = 512.75 0.1 K, PC = 8.120 0.02 MPa, and C = 271.6 3 kg m3 ). The essential effect of thermal decomposition of the methanol molecules on PVT behavior is observed at high temperatures (above 573 K). Acknowledgments

[6]

[7]

[8]

[9] [10]

[11]

[12] [13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

One of us, I.M.A., thanks the Physical and Chemical Properties Division at the National Institute of Standards and Technology for the opportunity to work as a Guest Researcher at NIST during the course of this research. We also thank Dr. G. Rabadanov for the chromatography analysis of the methanol sample before and after experiments. The part of this work was supported by the Grant of RFBR 05-08-18229-a. References
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