Eckhard Vogel

Reference Correlation of the Viscosity of Propane

A new representation of the viscosity of propane includes a zero-density correlation and an initial-density dependence correlation based on the kinetic theory of dilute gases and on the Rainwater–Friend theory. The higher density contributions of the residual viscosity in the representation are formed by a combination of double polynomials in density and reciprocal temperature, and a free-volume term with a temperature-dependent close-packed density. The full surface correlation is based on a set of primary experimental data selected as a result of a critical assessment of the available information from 37 original viscosity studies. The review refers to 96 citations altogether. The validity of the representation extends from the triple point to 600 K and 100 MPa in accordance with the modified Benedict–Webb–Rubin equation of state. The uncertainty of the representation varies from ±0.4% for the viscosity of the dilute gas phase between room temperature and 600 K, to about ±2.5% for the range 100–475 K up...

The viscosity and thermal conductivity of pure monatomic gases from their normal boiling point up to 5000 K in the limit of zero density and at 0.101325 MPa

The kinetic theory of gases in the limit of zero density and that of moderately dense gases is used to generate accurate tables of the viscosity and thermal conductivity of the pure monatomic gases for zero density and for a pressure of 0.101325 MPa. The theoretically‐based tables cover the temperature range from the normal boiling point of the relevant gas up to 5000 K. The associated uncertainties of the proposed data are detailed in the paper. A comparison of the correlated data with experimental results and some other recent correlations is given.

Ab initio potential energy curve for the helium atom pair and thermophysical properties of the dilute helium gas. II. Thermophysical standard values for low-density helium

A helium–helium interatomic potential energy curve determined from quantum-mechanical ab initio calculations and described with an analytical representation considering relativistic retardation effects (R. Hellmann, E. Bich, and E. Vogel, Molec. Phys. (in press)) was used in the framework of the quantum-statistical mechanics and of the corresponding kinetic theory to calculate the most important thermophysical properties of helium governed by two-body and three-body interactions. The second pressure virial coefficient as well as the viscosity and thermal conductivity coefficients, the last two in the so-called limit of zero density, were calculated for 3He and 4He from 1 to 10 000 K and the third pressure virial coefficient for 4He from 20 to 10 000 K. The transport property values can be applied as standard values for the complete temperature range of the calculations characterized by an uncertainty of ±0.02% for temperatures above 15 K. This uncertainty is superior to the best experimental measurements at ambient temperature.

New International Formulation for the Thermal Conductivity of H2O

The International Association for the Properties of Water and Steam (IAPWS) encouraged an extensive research effort to update the IAPS Formulation 1985 for the Thermal Conductivity of Ordinary Water Substance, leading to the adoption of a Release on the IAPWS Formulation 2011 for the Thermal Conductivity of Ordinary Water Substance. This paper describes the development and evaluation of the 2011 formulation, which provides a correlating equation for the thermal conductivity of water for fluid states from the melting temperature up to 1173 K and 1000 MPa with uncertainties from less than 1% to 6%, depending on the state point.

Ab initio potential energy curve for the neon atom pair and thermophysical properties for the dilute neon gas. II. Thermophysical properties for low-density neon

A neon–neon interatomic potential energy curve determined from quantum-mechanical ab initio calculations and described with an analytical representation (R. Hellmann, E. Bich, and E. Vogel, Molec. Phys. 106, 133 (2008)) was used in the framework of the quantum-statistical mechanics and of the corresponding kinetic theory to calculate the most important thermophysical properties of neon governed by two-body and three-body interactions. The second and third pressure virial coefficients as well as the viscosity and thermal conductivity coefficients, the last two in the so-called limit of zero density, were calculated for natural Ne from 25 to 10,000 K. Comparison of the calculated viscosity and thermal conductivity with the most accurate experimental data at ambient temperature shows that these values are accurate enough to be applied as standard values for the complete temperature range of the calculations characterized by an uncertainty of about ±0.1% except at the lowest temperatures.

Ab initio potential energy curve for the helium atom pair and thermophysical properties of dilute helium gas. I. Helium–helium interatomic potential

A helium–helium interatomic potential energy curve was determined from quantum-mechanical ab initio calculations. Very large atom-centred basis sets including a newly developed d-aug-cc-pV8Z basis set supplemented with bond functions and ab initio methods up to full CI were applied. The aug-cc-pV7Z basis set of Gdanitz (J. Chem. Phys. 113, 5145 (2000)) was modified to be more consistent with the aug-cc-pV5Z and aug-cc-pV6Z basis sets. The diagonal Born–Oppenheimer corrections as well as corrections for relativistic effects were also calculated. A new analytical representation of the interatomic potential energy was fitted to the ab initio calculated values. In a following paper this potential model will be used in the framework of quantum-statistical mechanics and of the corresponding kinetic theory to calculate the most important thermophysical properties of helium governed by two-body and three-body interactions.

Ab initio pair potential energy curve for the argon atom pair and thermophysical properties of the dilute argon gas. I. Argon–argon interatomic potential and rovibrational spectra

A neon–neon interatomic potential energy curve was derived from quantum-mechanical ab initio calculations using basis sets of up to t-aug-cc-pV6Z quality supplemented with bond functions and ab initio methods up to CCSDT(Q). In addition, corrections for relativistic effects were determined. An analytical potential function was fitted to the ab initio values and utilised to calculate the rovibrational spectra. The quality of the interatomic potential function was tested by comparison of the calculated spectra with experimental ones and those derived from other potentials of the literature. In a following paper the new interatomic potential is applied in the framework of the quantum-statistical mechanics and of the corresponding kinetic theory to determine selected thermophysical properties of neon governed by two-body and three-body interactions.

Ab initio virial equation of state for argon using a new nonadditive three-body potential

An ab initio nonadditive three-body potential for argon has been developed using quantum-chemical calculations at the CCSD(T) and CCSDT levels of theory. Applying this potential together with a recent ab initio pair potential from the literature, the third and fourth to seventh pressure virial coefficients of argon were computed by standard numerical integration and the Mayer-sampling Monte Carlo method, respectively, for a wide temperature range. All calculated virial coefficients were fitted separately as polynomials in temperature. The results for the third virial coefficient agree with values evaluated directly from experimental data and with those computed for other nonadditive three-body potentials. We also redetermined the second and third virial coefficients from the best experimental pρT data utilizing the computed higher virial coefficients as constraints. Thus, a significantly closer agreement of the calculated third virial coefficients with the experimental data was achieved. For different orders of the virial expansion, pρT data have been calculated and compared with results from high quality measurements in the gaseous and supercritical region. The theoretically predicted pressures are within the very small experimental errors of ±0.02% for p ≤ 12 MPa in the supercritical region near room temperature, whereas for subcritical temperatures the deviations increase up to +0.3%. The computed pressure at the critical density and temperature is about 1.3% below the experimental value. At pressures between 200 MPa and 1000 MPa and at 373 K, the calculated values deviate by 1% to 9% from the experimental results.

Calculation of the transport properties of carbon dioxide. I. Shear viscosity, viscomagnetic effects, and self-diffusion

Transport properties of pure carbon dioxide have been calculated from the intermolecular potential using the classical trajectory approach. Results are reported for shear viscosity, viscomagnetic coefficients, and self-diffusion in the dilute-gas limit and in the temperature range of 200–1500 K for the three recently proposed carbon dioxide potential energy hypersurfaces. Agreement with the measurements is, in general, within the experimental error. The calculations indicate that the corrections in the second-order approximation and those due to the angular-momentum polarization for the viscosity are small, <1% in the temperature range considered. The very good agreement of the calculated values for the Bukowski et al. potential energy hypersurface (1999) with the experimental viscosity data is consistent with the rigid-rotor assumption made in the calculations being reasonable for the three properties considered.

Calculation of the transport properties of carbon dioxide. II. Thermal conductivity and thermomagnetic effects

The transport properties of pure carbon dioxide have been calculated from the intermolecular potential using the classical trajectory method. Results are reported in the dilute-gas limit for thermal conductivity and thermomagnetic coefficients for temperatures ranging from 200 K to 1000 K. Three recent carbon dioxide potential energy hypersurfaces have been investigated. Since thermal conductivity is influenced by vibrational degrees of freedom, not included in the rigid-rotor classical trajectory calculation, a correction for vibration has also been employed. The calculations indicate that the second-order thermal conductivity corrections due to the angular momentum polarization (< 2%) and velocity polarization (< 1%) are both small. Thermal conductivity values calculated using the potential energy hypersurface by Bukowski et al. (1999) are in good agreement with the available experimental data. They underestimate the best experimental data at room temperature by 1% and in the range up to 470 K by 1%-3%, depending on the data source. Outside this range the calculated values, we believe, may be more reliable than the currently available experimental data. Our results are consistent with measurements of the thermomagnetic effect at 300 K only when the vibrational degrees of freedom are considered fully. This excellent agreement for these properties indicates that particularly the potential surface of Bukowski et al. provides a realistic description of the anisotropy of the surface.