Experimental setup to measure critical properties of pure and binary mixtures and their densities at different pressures and temperatures: Determination of the precision and uncertainty in the results

Abstract We describe an experimental setup to measure critical properties and density as a function of pressure and temperature. Critical temperature and critical pressure ( T c , P c ) are measured with a flow apparatus, and detected by critical opalescence. Precision in measuring critical points for pure compounds and binary mixtures are characterized in terms of repeatability and confidence interval. The volumetric properties are determined with a high-pressure vibrating-tube density meter, calibrated from 278.15 to 318.15 K at pressures up to 200 × 10 5  Pa. Density values are validated for pure compounds by determining the absolute and relative root-mean-square deviations to CO 2 data obtained from the Span and Wagner equations of state (EOS), and for binary mixtures by determining the relative mean standard deviation of density, s ¯ ρ r . Both the critical and volumetric experimental results have been compared with literature data and values obtained from the Peng–Robinson and Patel–Teja cubical equations of state.

[1]  W. Kay.  Liquid-Vapor Phase Equilibrium Relations in the Ethane-n-Heptane System , 1938 .

[2]  W. Kay,et al.  Critical constants of conformed mixtures , 1969 .

[3]  Daniel J. A. Rosenthal,et al.  Critical pressures and temperatures of isomeric alkanols , 1989 .

[4]  Jianguo Liu,et al.  Critical properties of binary and ternary mixtures of hexane+methanol, hexane+carbon dioxide, methanol+carbon dioxide and hexane+carbon dioxide+methanol , 2003 .

[5]  Syed S. H. Rizvi,et al.  Vapor-liquid equilibria in the ammonia-water system , 1987 .

[6]  R. Gani,et al.  New group contribution method for estimating properties of pure compounds , 1994 .

[7]  Amyn S. Teja,et al.  A NEW CUBIC EQUATION OF STATE FOR FLUIDS AND FLUID MIXTURES , 1982 .

[8]  W. Kay,et al.  Liquid-vapour equilibria in the iso-butanol—n-butanol, methanol—n-butanol and diethyl ether—n-butanol systems , 1955 .

[9]  G. Morrison.  Effect of water on the critical points of carbon dioxide and ethane , 1981 .

[10]  A. Teja,et al.  Critical temperatures and densities of isomeric alkanols with six to ten carbon atoms , 1988 .

[11]  P. Kolář,et al.  Experimental determination of the critical line for (carbon dioxide + ethane) and calculation of various thermodynamic properties for (carbon dioxide + n-alkane) using the PSRK model , 2000 .

[12]  A. Francesconi,et al.  Phase equilibriums and PVT data for the methane-methanol system to 300 MPa and 240.degree.C , 1981 .

[13]  W. Wagner,et al.  The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use , 2002 .

[14]  C. L. Young,et al.  The (gas + liquid) critical properties and phase behaviour of some binary alkanol (C2–C5) + alkane (C5–C12) mixtures , 2003 .

[15]  G. Morrison,et al.  Critical point measurements on nearly polydisperse fluids , 1984 .

[16]  D. Balzarini,et al.  Lorentz-Lorenz coefficient of ethane , 1974 .

[17]  D. R. Douslin,et al.  Pressure, volume, temperature relations of ethane , 1973 .

[18]  B. A. Grigoryev,et al.  Thermodynamic properties of n-hexane , 1988 .

[19]  J. Hannay.  IV. On the solubility of solids in gases. II , 1880, Proceedings of the Royal Society of London.

[20]  A. Mousa.  The physical properties of highly purified samples of propane and n-hexane , 1977 .

[21]  R. Smith,et al.  Phase equilibria in the n-hexane+diethylamine system , 1985 .

[22]  J. Arons,et al.  Vapour-liquid equilibria and critical phenomena in methanol + n-alkane systems , 1988 .

[23]  K. D. Luks,et al.  Partial miscibility behavior of the methane + ethane + n-docosane and the methane + ethane + n-tetradecylbenzene ternary mixtures , 1989 .

[24]  W. J. Dixon,et al.  Analysis of Extreme Values , 1950 .

[25]  Joseph Kestin,et al.  Thermophysical properties of fluid D2O , 1984 .

[26]  T. W. Loos,et al.  The pϱT properties of ethanol + hexane , 1995 .

[27]  F. Glaser,et al.  Untersuchungen über Dampfdruckkurven und kritische Daten einiger technisch wichtiger organischer Substanzen , 1957 .

[28]  W. M. Haynes,et al.  Thermophysical Properties of Propane from 85 to 700 K at Pressures to 70 MPa. Revision. , 1982 .

[29]  J. Zollweg,et al.  Vapor-liquid equilibrium in the binary system carbon dioxide + n-butane , 1989 .

[30]  T. Storvick,et al.  Phase Behavior from Enthalpy Measurements. , 1960 .

[31]  R. Fischer,et al.  Die Bestimmung der kritischen Temperatur auf dem Mikroschmelzpunktapparat , 1944 .

[32]  J. Kuenen.  XXVII. Experiments on the condensation and critical phenomena of some substances and mixtures , 1897 .

[33]  O. Maass,et al.  SOME PHYSICAL PROPERTIES OF HYDROCARBONS CONTAINING TWO AND THREE CARBON ATOMS. , 1921 .

[34]  D. Ambrose,et al.  Vapour pressures up to their critical temperatures of normal alkanes and 1-alkanols , 1989 .

[35]  Zhimin Liu,et al.  Measurement of critical points of the methylcyclohexane (MCH)–H2–CO2 system in the CO2-rich region , 2001 .

[36]  E. Brunner.  Fluid mixtures at high pressures I. Phase separation and critical phenomena of 10 binary mixtures of (a gas + methanol) , 1985 .

[37]  J. Gmehling,et al.  Experimental determination of critical data of mixtures and their relevance for the development of thermodynamic models , 2001 .

[38]  S. Young,et al.  LXXXIII.—The vapour pressures, specific volumes and critical constants of hexamethylene , 1899 .

[39]  H. V. Kehiaian,et al.  Enthalpies of vaporization of organic compounds : a critical review and data compilation , 1985 .

[40]  V. V. Sychev,et al.  Thermodynamic Properties of Ethane , 1987 .

[41]  E. Kiran,et al.  Solubility and demixing of polyethylene in supercritical binary fluid mixtures : carbon dioxide-cyclohexane, carbon dioxide-toluene, carbon dioxide-pentane , 1993 .

[42]  C. Tsonopoulos,et al.  Vapor-Liquid Critical Properties of Elements and Compounds. 2. Normal Alkanes , 1995 .

[43]  C. Young.  Gas-liquid critical properties of the cycloalkanes and their mixtures , 1972 .

[44]  Chuan Yi Tang,et al.  A 2.|E|-Bit Distributed Algorithm for the Directed Euler Trail Problem , 1993, Inf. Process. Lett..

[45]  Dominique Richon,et al.  An enhanced method to calibrate vibrating tube densimeters , 2001 .

[46]  D. Ambrose,et al.  The critical temperatures of forty organic compounds , 1960 .

[47]  M. Zander,et al.  Some thermodynamic properties of liquid ammonia: PVT data, vapor pressure, and critical temperature , 1979 .

[48]  J. Gallagher,et al.  Thermodynamic Properties of Ammonia , 1978 .

[49]  Andreas Martin,et al.  Application of fluid opacity for determining the phase behavior of binary mixtures near their critical loci – CO2 plus ethane and CO2 plus propane , 1999 .

[50]  Amyn S. Teja,et al.  The critical temperatures and densities of the n-alkanes from pentane to octadecane , 1990 .

[51]  B. Sage,et al.  Phase Equilibria in Hydrocarbon Systems V. Pressure-Volume-Temperature Relations and Thermal Properties of Propane , 1934 .

[52]  S. G. Mason,et al.  A STUDY OF THE COEXISTENCE OF THE LIQUID AND GASEOUS STATES OF AGGREGATION IN THE CRITICAL TEMPERATURE REGION. ETHYLENE , 1940 .

[53]  D. Peng,et al.  A New Two-Constant Equation of State , 1976 .

[54]  B. Sage,et al.  Phase Equilibria in Hydrocarbon Systems XVIII. Thermodynamic Properties of Ethane , 1937 .

[55]  W. Wagner,et al.  A New Equation of State for Carbon Dioxide Covering the Fluid Region from the Triple‐Point Temperature to 1100 K at Pressures up to 800 MPa , 1996 .

[56]  K. Ohgaki,et al.  Isothermal vapor-liquid equilibrium data for the ethane—carbon dioxide system at high pressures , 1977 .

[57]  E. Schmidt,et al.  Präzisionsbestimmungen des kritischen Punktes von Kohlensäure und Äthan durch Messung der Lichtbrechung , 1954 .

[58]  Daniel G. Friend,et al.  Thermophysical Properties of Ethane , 1991 .

[59]  E. Brunner.  Fluid mixtures at high pressures V. Phase separation and critical phenomena in 18 binary mixtures containing either pyridine or ethanoic acid , 1987 .

[60]  Daniel J. A. Rosenthal,et al.  Correlation of the critical properties of alkanes and alkanols , 1990 .

[61]  C. Wormald,et al.  Excess enthalpies and excess volumes of (0.5CO2+ 0.5C2H6) in the supercritical region , 1988 .

[62]  C. P. Hicks,et al.  Gas-liquid critical temperatures of mixtures: benzene + n-alkanes and hexafluorobenzene + n-alkanes , 1971 .

[63]  D. Ambrose,et al.  The critical temperatures and pressures of thirty organic compounds , 1974 .

[64]  W. Kay.  P-T-x Diagrams in the Critical Region. Acetone-n-Alkane Systems , 1964 .

[65]  S. G. Mason,et al.  COEXISTENCE PHENOMENA IN THE CRITICAL REGION: II. INFLUENCE OF GRAVITY ON THE COEXISTENCE CURVES OF ETHANE, ETHYLENE, AND XENON , 1953 .

[66]  H. J. Van Der Kooi,et al.  Vapor-liquid equilibria for the system ammonia + water up to the critical region. , 1990 .

[67]  M. Uematsu,et al.  Critical parameters for ammonia , 2005 .

[68]  J. S. Rowlinson,et al.  The physical properties of some fluorine compounds and their solutions. Part 2.—The system sulphur hexafluoride+propane , 1955 .

[69]  A. Diefenbacher,et al.  Critical properties (pc, Tc, and ρc) and phase equilibria of binary mixtures of CO2, CHF3, CH2F2, and SF6 , 2001 .

[70]  R. Smith,et al.  The critical temperatures of isomeric pentanols and heptanols , 1986 .

[71]  A. Teja,et al.  A study of the volumetric and phase behavior of binary systems. Part I. Critical properties of propane‐perfluorocyclobutane mixtures , 1982 .

[72]  Barry N. Taylor,et al.  Guidelines for Evaluating and Expressing the Uncertainty of Nist Measurement Results , 2017 .

[73]  W. Kay,et al.  Liquid-Vapor Equilibrium Relations in the Ethane-Cyclohexane System , 1956 .

[74]  W. G. Cochran.  The $\chi^2$ Test of Goodness of Fit , 1952 .

[75]  W. Kay,et al.  The Critical Properties of Binary Hydrocarbon Systems , 1972 .

[76]  P. Sliwinski.  Die Lorentz-Lorenz-Funktion von dampfförmigem und flüssigem Äthan, Propan und Butan , 1969 .

[77]  A. Zawisza.  High-pressure liquid-vapour equilibria, critical state, and p(Vm, T, x) to 448.15 K and 4.053 MPa for {xC6H14 + (1−x)CH3OH} , 1985 .

[78]  J. Kuenen.  LXXX. On the mutual solubility of liquids.—II , 1903 .

[79]  A. E. Mather,et al.  Azeotropy and critical behavior in the system propane-hydrogen sulfide , 1995 .

[80]  W. L. Marshall,et al.  Liquid-vapor critical temperatures of several aqueous-organic and organic-organic solution systems , 1974 .

[81]  R. Craven,et al.  Ideal-gas and saturation properties of methanol , 1986 .

[82]  J. M. Skaates,et al.  The phase relations of binary systems that form azeotropes: N-alkyl alcohol-benzene systems: Methanol through n-butanol , 1964 .

[83]  Lixiong Li,et al.  Gas-liquid critical properties of methylamine + nitrous oxide and methylamine + ethylene binary mixtures , 1988 .

[84]  J. Beattie,et al.  The Critical Constants of Ethane , 1939 .

[85]  Critical constants of n-alkanes with from 17 to 24 carbon atoms , 1994 .

[86]  W. Kay,et al.  Virial coefficients of ethanol from 373.07 to 473.15 K , 1984 .

[87]  V. Tsochev,et al.  Critical temperatures and pressures and high temperature vapour pressures of seven alcohols , 1990 .

[88]  C. Domb,et al.  The Critical Point , 1996 .

[89]  J. Dewar.  XXVIII. On the liquefaction of oxygen and the critical volumes of fluids , 1884 .

[90]  J. Sengers,et al.  Thermodynamic properties of ammonia in the critical region , 1999 .

[91]  W. Kay.  The vapor pressures and saturated liquid and vapor densities of the isomeric hexanes. , 1946, Journal of the American Chemical Society.

[92]  A. Mousa,et al.  The critical constants of binary mixtures of certain perfluoro-compounds with alkanes , 1972 .

[93]  M. L. Mcglashan,et al.  The vapour pressure from 451 K to the critical temperature, and the critical temperature and critical pressure, of cyclohexane , 1978 .

[94]  E. Brunner.  Fluid mixtures at high pressures. VI: Phase separation and critical phenomena in 18 (n-alkane+ammonia) and 4(n-alkane+methanol) mixtures , 1988 .

[95]  A. Teja,et al.  Vapor-Liquid Critical Properties of Elements and Compounds. 4. Aliphatic Alkanols , 1995 .

[96]  J. Hannay,et al.  I. On the solubility of solids in gases , 1880, Proceedings of the Royal Society of London.

[97]  Robert C. Reid,et al.  Estimation of critical properties with group contribution methods , 1984 .

[98]  T. W. Price.  XX.—Osmotic pressure of alcoholic solutions. Part I. Vapour pressures and densities , 1915 .

[99]  E. Brunner.  Fluid mixtures at high pressures II. Phase separation and critical phenomena of (ethane + an n-alkanol) and of (ethene + methanol) and (propane + methanol) , 1985 .

[100]  S. B. Kiselev,et al.  Extended law of corresponding states and thermodynamic properties of binary mixtures in and beyond the critical region , 1997 .

[101]  J. S. Rowlinson,et al.  Gas-liquid critical temperatures of binary mixtures. Part 2 , 1960 .

[102]  K. Khilar,et al.  MEASUREMENT OF THE CRITICAL-TEMPERATURES AND CRITICAL PRESSURES OF SOME THERMALLY STABLE OR MILDLY UNSTABLE ALKANOLS , 1991 .

[103]  W. Kay,et al.  Liquid-Vapor Equilibrium Relations in Binary Systems - Propane - Hydrogen Sulfide System. , 1953 .

[104]  Amyn S. Teja,et al.  The critical properties of n‐alkanes using a low‐residence time flow apparatus , 1989 .

[105]  A. Teja,et al.  The critical properties of dilute n-alkane mixtures , 1993 .

[106]  P. Skripov,et al.  Measurement of the critical properties of thermally unstable substances and mixtures by the pulse-heating method , 1993 .

[107]  A. Teja,et al.  Study of the critical and azeotropic behavior of binary mixtures. 1. Critical states of perfluoromethylcyclohexane-isomeric hexane systems , 1980 .

[108]  B. Sage,et al.  Volumetric and phase behavior in the hydrogen–n‐hexane system , 1957 .

[109]  D. Cheng.  Critical temperatures and volumes of some binary systems , 1963 .

[110]  G. C. Schmidt.  Ueber die kritischen Temperaturen von Flüssigkeitsgemischen , 1891 .

[111]  R. Sadus,et al.  Phase behaviour of 1-alkanol + alkane mixtures: gas-liquid critical temperatures , 1991 .

[112]  Thomas E. Daubert,et al.  Vapor−Liquid Critical Properties of Elements and Compounds. 5. Branched Alkanes and Cycloalkanes , 1996 .

[113]  W. Kay.  Liquid-Vapor Equilibrium Relations in Binary Systems THE EHANE-n-BUTANE SYSTEM , 1940 .

[114]  J. Ely,et al.  Thermophysical Properties of Fluids. II. Methane, Ethane, Propane, Isobutane, and Normal Butane , 1987 .

[115]  W. Wagner,et al.  Measurement and correlation of the (pressure, density, temperature) relation of carbon dioxide I. The homogeneous gas and liquid regions in the temperature range from 217 K to 340 K at pressures up to 9 MPa , 1990 .

[116]  R. Singh,et al.  Critical Constants of n‐Butanol , 1955 .

[117]  R. H. Harrison,et al.  Pressure-volume-temperature relations of propane , 1982 .

[118]  Hwayong Kim,et al.  Isothermal vapor–liquid equilibria for ethanol and n-pentane system at the near critical region , 2000 .

[119]  J. Gmehling,et al.  Experimental determination of critical points of pure components and binary mixtures using a flow apparatus , 1999 .

[120]  L. A. Weber,et al.  Simple apparatus for vapor-liquid equilibrium measurements with data for the binary systems of carbon dioxide with n-butane and isobutane , 1989 .

[121]  H. B. Palmer.  Schlieren Studies of the Critical Region , 1954 .

[122]  Zhimin Liu,et al.  Critical points and phase behavior of toluene-CO2 and toluene-H2-CO2 mixture in CO2-rich region , 2000 .

[123]  K. Ohgaki,et al.  Pressure-density-temperature (p-p-T) relations of CHF3, N2O, and C3H6 in the critical region , 1990 .

[124]  W. Ramsay,et al.  On Evaporation and Dissociation. Part VIII. A Study of the Thermal Properties of Propyl Alcohol , 2022 .

[125]  John R. Griswold,et al.  Ethanol-Water System - Vapor-Liquid Properties at High Pressure , 1943 .

[126]  A. Sivaraman,et al.  Sonic speed and critical point measurements in ethane by the acoustic resonance method , 1992 .

[127]  Huiyun Lu,et al.  IV. The system ethane-propylene , 1941, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[128]  William Ramsay,et al.  III. On evaporation and dissociation.—Part II. A study of the thermal properties of alcohol , 1886, Philosophical Transactions of the Royal Society of London.

[129]  M. J. Richardson,et al.  The solubility of mercury in gases at moderate pressures , 1957 .

[130]  H. Kratzke.  Thermodynamic quantities for propane 1. The vapour pressure of liquid propane , 1980 .

[131]  D. Ambrose,et al.  681. Thermodynamic properties of organic oxygen compounds. Part IX. The critical properties and vapour pressures, above five atmospheres, of six aliphatic alcohols , 1963 .

[132]  C. J. Pings,et al.  Viscosity of xenon and ethane in the critical region , 1974 .

[133]  M. Uematsu,et al.  Critical parameters of {xCO2+ (1 −x)CHF3} forx= (1.0000, 0.7496, 0.5013, and 0.2522) , 1996 .

[134]  Eric W. Lemmon,et al.  Thermophysical Properties of Fluid Systems , 1998 .

[135]  W. Kay,et al.  Liquid-Vapor Equilibrium Relations in Ethane-Hydrogen Sulfide System , 1953 .

[136]  D. Ambrose,et al.  The critical temperatures of some hydrocarbons and pyridine bases , 1957 .