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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    International journal of thermophysics 14 (1993), S. 1-32 
    ISSN: 1572-9567
    Keywords: critical phenomena ; equation of state ; ethane ; methane ; sound velocity ; specific heat ; thermodynamic properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract An improved parametric equation for the thermodynamic properties of fluids is presented that incorporates the crossover from singular thermodynamic behavior in the immediate vicinity of the critical point to regular thermodynamic behavior far away from the critical point. Based on a comparison with experimental data for ethane and methane, it is demonstrated that the crossover model is capable of representing the thermodynamic properties of fluids in a large range of temperatures and densities around the critical point.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    International journal of thermophysics 20 (1999), S. 563-588 
    ISSN: 1572-9567
    Keywords: binary mixtures ; critical region ; D2O ; equation of state ; H2O ; phase behavior ; thermodynamic properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract A parametric crossover model is adapted to represent the thermodynamic properties of pure D2O in the extended critical region. The crossover equation of state for D2O incorporates scaling laws asymptotically close to the critical point and is transformed into a regular classical expansion far from the critical point. An isomorphic generalization of the law of corresponding states is applied to the prediction of thermodynamic properties and the phase behavior of D2O + H2O mixtures over a wide region around the locus of vapor-liquid critical points. A comparison is made with experimental data for pure D2O and for the D2O + H2O mixture. The equation of state yields a good representation of thermodynamic property data in the range of temperatures 0.8T c(x)≤T≤1.5T c(x) and densities 0.35ρc(x)≤ρ≤1.65ρc(x).
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    International journal of thermophysics 21 (2000), S. 1373-1405 
    ISSN: 1572-9567
    Keywords: associating fluids, critical state ; crossover theory ; equation of state ; enthalpies ; heat capacities ; n-alkanols ; thermodynamic properties ; speed of sound ; vapor–liquid equilibrium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract In this work we have developed a new equation of state (EOS) for propan-1-ol on the basis of the crossover modification (CR) of the statistical-associating-fluid-theory (SAFT) EOS recently developed and applied to n-alkanes. The CR SAFT EOS reproduces the nonanalytical scaling laws in the asymptotic critical region and reduces to the analytical-classical SAFT EOS far away from the critical point. Unlike the previous crossover EOS, the new CR SAFT EOS is based on the parametric sine model for the universal crossover function and is able to represent analytically connected van der Waals loops in the metastable fluid region. The CR SAFT EOS contains 10 system-dependent parameters and allows an accurate representation of the thermodynamic properties of propan-1-ol over a wide range thermodynamic states including the asymptotic singular behavior in the nearest vicinity of the critical point. The EOS was tested against experimental isochoric and isobaric specific heats, speed of sound, PVT, and VLE data in and beyond the critical region. In the one-phase region, the CR SAFT equation represents the experimental values of pressure with an average absolute deviation (AAD) of less than 1% in the critical and supercritical regions and the liquid densities with an AAD of about 1%. A corresponding states principle is used for the extension of the new CR SAFT EOS for propan-1-ol to higher n-alkanols.
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  • 4
    ISSN: 1572-9567
    Keywords: critical phenomena ; equation of state ; ethane ; methane ; plait point ; thermodynamic properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We present an equation of state for the thermodynamic properties of mixtures of methane and ethane in the critical region that incorporates the crossover from singular thermodynamic behavior near the locus of vapor-liquid critical points to regular thermodynamic behavior outside the critical region. The equation of state yields a satisfactory representation of the thermodynamic-property data for the mixtures in a large range of temperatures and densities.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    International journal of thermophysics 6 (1985), S. 465-481 
    ISSN: 1572-9567
    Keywords: critical phenomena ; equation of state ; scaling laws ; steam ; thermodynamic properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract A scaled equation of state is proposed for real fluids in the critical region which incorporates asymmetry with respect to the critical isochore. In the range of reduced densities 0.65⩽(θ/θ c)⩽1.4 and for reduced temperatures (T/T c)⩽1.2, the equation represents P-V-T data for steam within the experimental accuracy.
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  • 6
    ISSN: 1612-1112
    Keywords: Gas-solid chromatography ; Graphitized thermal carbon black ; Thermodynamics of adsorption ; Nitrogen compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary To study the role of the nitrogen atom in various valence states in the adsorption of nitrogen-containing molecules on the surface of hydrogen-treated graphitized thermal carbon black (HGTCB) gas chromatography was applied to determine the thermodynamic characteristics of adsorption: Henry's constants and heats of adsorption at zero surface coverage of nitriles, amines and indols on HGTCB. Adsorption characteristics of nitrogen-containing organic compounds and corresponding hydrocarbons are compared. It is shown that the logarithm of the retention volume and the heat of adsorption of n-alkylamines and n-alkylnitriles linearly depend on the number of carbon atoms in the molecule and on the average polarisability of the molecule. Relationship has been established between the Henry's constant as well as the heat of adsorption and the geometry of the molecule's disposition on HGTCB surface. Examples are given for the separation of a number of amines on the basis of the geometry of their molecules.
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  • 7
    ISSN: 1612-1112
    Keywords: Gas-solid chromatography ; Gas-adsorption chromatography ; Henry's constants measurements, calculations ; Aromatic, cyclic hydrocarbons ; Chromatoscopy of tetralin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention volumes at zero sample size (Henry's constants) on graphitized thermal carbon black have been measured at a number of temperatures for benzene, all its methyl-substituted and some of alkyl-substituted derivatives, naphthalene, diphenyl, phenanthrene, anthracene, tetralin, cis- and trans-decalin, cyclohexane, adamantane and diamantane. The earlier published thermodynamic characteristics of adsorption of the aromatic hydrocarbons have been revised. A molecular statistical calculation of thermodynamic characteristics of adsorption using the atom-atom approximation for the energy of intermolecular interaction between adsorbate and adsorbent has been carried out for polycyclic hydrocarbons: adamantane, diamantane, cis- and trans-decalin. The measured retention volumes of tetralin have been used for the calculation of some parameters of geometric structure of the molecule.
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  • 8
    ISSN: 1612-1112
    Keywords: Geometric isomers ; Gas-solid chromatography ; Graphitized carbon black ; Packed capillaries ; Polycyclic hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Using the example of perhydrophenanthrene, perhydroanthracene and cyclopentanodecalin isomers a possibility is shown to use packed capillary columns containing graphitized thermal carbon black for a complete separation of high-boiling mixtures of polycyclic saturated hydrocarbon isomers in accordance with the geometric structure of their molecules.
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  • 9
    ISSN: 1612-1112
    Keywords: Gas-solid chromatography ; Graphitized carbon black ; Aromatic hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This paper defines values of retention volumes for zero surface coverage (Henry's constant) at different temperatures, retention indices and variations of the internal energy (differential heats of adsorption) of diphenyl and its alkyl derivatives, terphenyls, diphenylmethane, triphenylmethane, diphenylethanes and fluorene on graphitized thermal carbon black (GTCB). Adsorption on GTCB takes place in accordance with the geometry of these molecules, the strongest adsorption being observed for para-terphenyl with least inhibited internal rotation of the molecule, while the weakest adsorption occurs for 2,6,2′,6′-tetramethyldiphenyl with the most inhibited internal rotation of the molecules. The flat molecules of fluorene are adsorbed on GTCB more readily than the nonflat molecules of diphenylmethane.
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  • 10
    ISSN: 1612-1112
    Keywords: Gas-solid chromatography ; Retention on graphitized carbon black ; Phenylcyclanes, phenyl- and biphenylalkenes and ; alkines, bicyclohexyl, bicyclohexylmethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention volume values for zero cample size (Henry's constants) at different temperatures, retention indices and differential adsorption heats of phenylethylene, phenylacetylene, C9–C12 phenylcyclanes, biphenylethylenes, biphenylacetylene, bicyclohexyl and bicyclohexylmethane have been determined on graphitized thermal carbon black (GTCB). The molecules of all these hydrocarbons are capable of internal rotation. The values of the thermodynamic adsorption characteristics of phenylcyclanes increase with increasing number of carbon atoms in the cycle. Bicyclohexyl is retained on GTCB considerably weaker than biphenyl while bicyclohexylmethane is retained stronger than biphenylmethane. Symmetric and nonsymmetric biphenylethylenes are retained much stronger than the corresponding biphenylethanes. Phenylethylene (styrene) and trans-biphenylethylene (trans-stilbene) are stronger retained on GTCB than phenylacetylene and biphenylacetylene (tolane), respectively. The relationship between the structure of these molecules and their retention on GTCB is discussed.
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