Isochoric heat-capacity measurements for pure methanol are presented as a function of temperature at fixed densities between 136 and 750 kg·m−3. The measurements cover a range of temperatures from 300 to 556 K. The coverage includes the one- and two-phase regions, the coexistence curve, the near-critical, and the supercritical regions. A high-temperature, high-pressure, adiabatic, and nearly constant-volume calorimeter was used for the measurements. Uncertainties of the heat-capacity measurements are estimated to be 2–3% depending on the experimental density and temperature. Temperatures at saturation, T S(ρ), for each measured density (isochore) were measured using a quasi-static thermogram technique. The uncertainty of the phase-transition temperature measurements is 0.02 K. The critical temperature and the critical density for pure methanol were extracted from the saturated data (T S,ρS) near the critical point. For one near-critical isochore (398.92 kg·m−3), the measurements were performed in both cooling and heating regimes to estimate the effect of thermal decomposition (chemical reaction) on the heat capacity and phase-transition properties of methanol. The measured values of C V and saturated densities (T S,ρS) for methanol were compared with values calculated from various multiparametric equations of state (EOS) (IUPAC, Bender-type, polynomial-type, and nonanalytical-type), scaling-type (crossover) EOS, and various correlations. The measured C V data have been analyzed and interpreted in terms of extended scaling equations for the selected thermodynamic paths (critical isochore and coexistence curve) to accurately calculate the values of the asymptotical critical amplitudes (\(A_0^\pm\) and B 0).
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References
Yerlett T.K., Wormald C.J. (1986). J. Chem. Thermodyn. 18:719
Straty G.C., Palavra A.M.F., Bruno T.J. (1986). Int. J. Thermophys. 7:1077
R. Ta’ani, Dr. Ing. Thesis (Karlsruhe, 1976).
I. M. Abdulagatov, V. I. Dvorynchikov, M. M. Aliev, and A. N. Kamalov, in Steam, Water, and Hydrothermal Systems, Proc. 13th Int. Conf. Prop. Water and Steam, P. R. Tremaine, P. G. Hill, D. E. Irish, and P. V. Balakrishnan, eds. (NRC Research Press, Ottawa, 2000), pp.157–164.
Bruno T.J., Straty G.C. (1986). J. Res. NBS 91:135
A. R. Bazaev, I. M. Abdulagatov, J. W. Magee, and E. A. Bazaev, J. Supercrit. Fluids (in press).
Ting S.S.T., Macnaughton S.J., Tomasko D.L., Foster N.R. (1993). Ind. Eng. Chem. Res. 32:1471
Gurdial G.S., Macnaughton S.J., Tomasko D.L., Foster N.R. (1993). Ind. Eng. Chem. Res. 32:1488
Dobbs J.M., Wong J.M., Lahiere R.J., Johnston K.P. (1987). Ind. Eng. Chem. Res. 26:56
Ekart M.P., Bennett K.L., Ekart S.M., Gurdial G.S., Liotta C.L., Eckert C.A. (1993). AIChE J. 39:235
Dooley K.M., Kao Ch.-P., Gambrell R.P., Knopf F.C. (1987). Ind. Eng. Chem. Res. 26:2058
K. M. De Reuck and R. J. B. Craven, Methanol. International Thermodynamic Tables of the Fluid State-12 (Blackwell, Oxford, 1993).
Eubank P.T. (1970). Chem. Eng. Symp. Ser. 66:16
Abdulagatov I.M., Kiselev S.B., Ely J.F., Polikhronidi N.G., Abdurashidova A. (2005). Int. J. Thermophys. 26:1327
Aliev M.M., Magee J.W., Abdulagatov I.M. (2003). Int. J. Thermophys. 24:1527
Kitajima H., Kagawa N., Endo H., Tsuruno S., Magee J.W. (2003). J. Chem. Eng. Data 48:1583
Kuroki T., Kagawa N., Endo H., Tsuruno S., Magee J.W. (2001). J. Chem. Eng. Data 46:1101
Ya. M. Suleimanov, Ph.D. Thesis (Power Eng. Research Inst., Baku, 1971).
Ramsay W., Young S. (1887). Phyl. Trans. Roy. Soc. (London) A 178:313
Efremov Yu.V. (1966). Russ. J. Phys. Chem. 40:1240
Cibulka I. (1993). Fluid Phase Equilib. 89:1
Machado J.R.S., Streett W.B. (1983). J. Chem. Eng. Data 28:218
Goodwin R.D. (1987). J. Phys. Chem. Ref. Data 16:799
Zubarev V.N., Bagdonas A.V. (1967). Teploenergetika 4:79
W. E. Donham, Ph.D. Thesis (Ohio State University, Columbus, Ohio, 1953).
Kay W.B., Donham W.E. (1955). Chem. Eng. Sci. 4:1
A. D. Kozlov, Methanol: Equations for Calculation of Thermophysical Properties, private communication (Russian Research Center for Standardization, Information and Certification of Materials, Moscow, Russia, 2002).
Straty G.C., Ball M.J., Bruno T.J. (1988). J. Chem. Eng. Data 33:115
Hales J.L., Ellender J.H. (1976). J. Chem. Thermodyn. 8:1177
Gude M., Teja A.S. (1995). J. Chem. Eng. Data 40:1025
Kh. I. Amirkhanov, G. V. Stepanov, and B. G. Alibekov, Isochoric Heat Capacity of Water and Steam (Amerind Pub. Co., New Delhi, 1974).
Polikhronidi N.G., Abdulagatov I.M., Magee J.W., Stepanov G.V. (2001). Int. J. Thermophys. 22:189
Polikhronidi N.G., Abdulagatov I.M., Magee J.W., Stepanov G.V. (2002). Int. J. Thermophys. 23:745
Polikhronidi N.G., Abdulagatov I.M., Magee J.W., Stepanov G.V. (2003). Int. J. Thermophys. 24:405
Polikhronidi N.G., Batyrova R.G., Abdulagatov I.M. (2000). Int. J. Thermophys. 21:1073
Mursalov B.A., Abdulagatov I.M., Dvoryanchikov V.I., Kiselev S.B. (1999). Int. J. Thermophys. 20:1497
Polikhronidi N.G., Batyrova R.G., Abdulagatov I.M., Magee J.W., Stepanov G.V. (2004). J. Supercrit. Fluids 33:209
Polikhronidi N.G., Abdulagatov I.M., Magee J.W., Batyrova R.G. (2001). J. Chem. Eng. Data 46:1064
Abdulagatov I.M., Polikhronidi N.G., Batyrova R.G. (1994). J. Chem. Thermodyn. 26:1031
Polikhronidi N.G., Batyrova R.G., Abdulagatov I.M. (2000). Fluid Phase Equilib. 175:153
Polikhronidi N.G., Abdulagatov I.M., Batyrova R.G. (2002). Fluid Phase Equilib. 201:269
Vargaftik N.B. (1983). Handbook of Physical Properties of Liquids and Gases, 2nd edn. Hemisphere, New York
Wagner W., Pruß A. (2002). J. Phys. Chem. Ref. Data 31:387
Keyes F.G., Smith L.B. (1933). Proc. Amer. Acad. Arts Sci. 68:505
Kamilov I.K., Stepanov G.V., Abdulagatov I.M., Rasulov A.R., Milikhina E.I. (2001). J. Chem. Eng. Data 46:1556
Abdulagatov I.M., Mursalov B.A., Dvoryanchikov V.I. (2000). J. Chem. Eng. Data 45:1133
Valyashko V.M., Abdulagatov I.M., Levelt-Sengers J.H.M. (2000). J. Chem. Eng. Data 45:1139
Ya. R. Chashkin, V. A. Smirnov, and A. V. Voronel, Thermophysical Properties of Substances and Materials, (Moscow, GSSSD, 1970), Vol. 2, p. 139.
A. V. Voronel, in Phase Transitions and Critical Phenomena, C. Domb and M. S. Green, eds. (Academic Press, London, 1974), Vol. 5, p. 343.
J. V. Sengers and J. M. H. Levelt Sengers, Progress in Liquid Physics, C.A. Croxton, ed. (Wiley, New York, 1978).
Sengers J.V., Levelt Sengers J.M.H. (1986). Ann. Rev. Phys. Chem. 37:189
Lemmon E.W., Span R. (2006). J. Chem. Eng. Data 51:785
Polt A., Platzer B., Maurer G. (1992). Chem. Tech. (Leipzig) 44:216
M. E. Fisher, in Critical Phenomena, Lectures Notes in Physics, F. J. W. Hahne, ed. (Springer, Berlin, 1988), Vol. 186, p. 1
M. A. Anisimov and J. V. Sengers, in Equations of State for Fluids and Fluid Mixtures, J. V. Sengers, R. F. Kayser, C. J. Peters, and H. J. White Jr., eds. (Elsevier, Amsterdam, 2000).
Greer S.C., Moldover M.R. (1981). Ann. Rev. Phys. Chem. 32:233
Anisimov M.A. (1991). Critical Phenomena in Liquids and Liquid Crystals. Gordon and Breach, Philadelphia
M. Levy, J. C. Le Guillou, and J. Zinn-Justin, eds., Phase Transitions, Cargese 1980 (Plenum, New York, 1982).
Liu A.J., Fisher M.E. (1989). Physica A 156:35
Bagnuls C., Bervilliev C., Meiron D.I., Nickel B.C. (1987). Phys. Rev. B 35:3585
Wegner F.J. (1972). Phys. Rev. B 5:4529
Ley -Koo M., Green M.S. (1981). Phys. Rev. A 23:2650
Saul D.M., Wortis M., Jasnow D. (1975). Phys. Rev. B 11:2571
Camp W.J., Van Dyke J.P. (1975). Phys. Rev. B 11:2579
Fisher M.E., Zinn S.-Y., Upton P.J. (1999). Phys. Rev. B59:14533
Guida R., Zinn-Justin J. (1998). J. Phys. A Math Gen. 31:8103
Nicoll J.F. (1981). Phys. Rev. A 24:2203
Hensel F. (1995). Adv. Phys. 44:3
Mermin N.D. (1971). Phys. Rev. Lett. 26:169
Rehr J.J., Mermin N.D. (1973). Phys. Rev. A 8:472
Widom B., Rowlinson J.S. (1970). J. Chem. Phys. 52:1670
Fisher M.E., Orkoulas G. (2000). Phys. Rev. Lett. 85:696
Orkoulas G., Fisher M.E., Ustün C. (2000). J. Chem. Phys. 113:7530
Young S. (1910). Sci. Proc. Roy. Dublin Soc. 21:374
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Polikhronidi, N.G., Abdulagatov, I.M., Stepanov, G.V. et al. Isochoric Heat-Capacity Measurements for Pure Methanol in the Near-Critical and Supercritical Regions. Int J Thermophys 28, 163–193 (2007). https://doi.org/10.1007/s10765-007-0164-4
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DOI: https://doi.org/10.1007/s10765-007-0164-4