Search

A four-dimensional potential energy surface (PES) for the interaction between a rigid carbon dioxide molecule and a rigid nitrogen molecule was constructed based on quantum-chemical ab initio calculations up to the coupled-cluster level with single, double, and perturbative triple excitations. Interaction energies for a total of 1893 points on the PES were calculated using the counterpoise-corrected supermolecular approach and basis sets of up to quintuple-zeta quality with bond functions. The interaction energies were extrapolated to the complete basis set limit, and an analytical site–site potential function with seven sites for carbon dioxide and five sites for nitrogen was fitted to the interaction energies. The CO2—N2 cross second virial coefficient as well as the dilute gas shear viscosity, thermal conductivity, and binary diffusion coefficient of CO2—N2 mixtures were calculated for temperatures up to 2000 K to validate the PES and to provide reliable reference values for these important properties. The calculated values are in very good agreement with the best experimental data. [ABSTRACT FROM AUTHOR]

The thermal conductivity of low-density CH4-N2 gas mixtures has been calculated by means of the classical trajectory method using state-of-the-art intermolecular potential energy surfaces for the CH4-CH4, N2-N2, and CH4-N2 interactions. Results are reported in the temperature range from 70 K to 1200 K. Since the thermal conductivity is influenced by the vibrational degrees of freedom of the molecules, which are not included in the rigid-rotor classical trajectory computations, a new correction scheme to account for vibrational degrees of freedom in a dilute gas mixture is presented. The calculations show that the vibrational contribution at the highest temperature studied amounts to 46% of the total thermal conductivity of an equimolar mixture compared to 13% for pure nitrogen and 58% for pure methane. The agreement with the available experimental thermal conductivity data at room temperature is good, within ±1.4%, whereas at higher temperatures, larger deviations up to 4.5% are observed, which can be tentatively attributed to deteriorating performance of the measuring technique employed. Results are also reported for the magnitude and temperature dependence of the rotational collision number, Zrot, for CH4 relaxing in collisions with N2 and for N2 relaxing in collisions with CH4. Both collision numbers increase with temperature, with the former being consistently about twice the value of the latter. [ABSTRACT FROM AUTHOR]

The viscomagnetic effect for two linear molecules, N2 and CO2, has been calculated in the dilute-gas limit directly from the most accurate ab initio intermolecular potential energy surfaces presently available. The calculations were performed by means of the classical trajectory method in the temperature range from 70 K to 3000 K for N2 and 100 K to 2000 K for CO2, and agreement with the available experimental data is exceptionally good. Above room temperature, where no experimental data are available, the calculations provide the first quantitative information on the magnitude and the behavior of the viscomagnetic effect for these gases. In the presence of a magnetic field, the viscosities of nitrogen and carbon dioxide decrease by at most 0.3% and 0.7%, respectively. The results demonstrate that the viscomagnetic effect is dominated by the contribution of the jj polarization at all temperatures, which shows that the alignment of the rotational axes of the molecules in the presence of a magnetic field is primarily responsible for the viscomagnetic effect. [ABSTRACT FROM AUTHOR]

The transport properties in the dilute gas limit have been calculated by the classical-trajectory method for a gas consisting of chain-like molecules. The molecules were modelled as rigid chains consisting of spherical segments that interact through a combination of site-site Lennard-Jones 12-6 potentials. Results are reported for shear viscosity, self-diffusion, and thermal conductivity for chains consisting of 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, and 16 segments in the reduced temperature range of 0.3 - 50. The results indicate that the transport properties increase with temperature and decrease with chain length. At high temperatures the dependence of the transport properties is governed effectively by the repulsive part of the potential. No simple scaling with chain length has been observed. The higher order correction factors are larger than observed for real molecules so far, reaching asymptotic values of 1.019 - 1.033 and 1.060 - 1.072 for viscosity and thermal conductivity, respectively. The dominant contribution comes from the angular momentum coupling. The agreement with molecular dynamics calculations for viscosity is within the estimated accuracy of the two methods for shorter chains. However, for longer chains differences of up to 7% are observed. [ABSTRACT FROM AUTHOR]

New expressions for the viscosity of liquid mixtures, consisting of chain-like molecules, are derived by means of Enskog-type analysis. The molecules of the fluid are modelled as chains of equally sized, tangentially joined, and rigid spheres. It is assumed that the collision dynamics in such a fluid can be approximated by instantaneous collisions. We determine the molecular size parameters from the viscosity of each pure species and show how the different effective parameters can be evaluated by extending the Vesovic-Wakeham (VW) method. We propose and implement a number of thermodynamically consistent mixing rules, taking advantage of SAFT-type analysis, in order to develop the VW method for chain molecules. The predictions of the VW-chain model have been compared in the first instance with experimental viscosity data for octane-dodecane and methane-decane mixtures, thus, illustrating that the resulting VW-chain model is capable of accurately representing the viscosity of real liquid mixtures. [ABSTRACT FROM AUTHOR]

Transport properties of dilute water vapor have been calculated in the rigid-rotor approximation using four different potential energy hypersurfaces and the classical-trajectory method. Results are reported for shear viscosity, self-diffusion, thermal conductivity, and volume viscosity in the dilute-gas limit for the temperature range of 250–2500 K. Of these four surfaces the CC-pol surface of Bukowski et al. [J. Chem. Phys. 128, 094314 (2008)] is in best accord with the available measurements. Very good agreement is found with the most accurate results for viscosity in the whole temperature range of the experiments. For thermal conductivity the deviations of the calculated values from the experimental data increase systematically with increasing temperature to around 5% at 1100 K. For both self-diffusion and volume viscosity, the much more limited number of available measurements are generally consistent with the calculated values, apart from the lower temperature isotopically labeled diffusion measurements. [ABSTRACT FROM AUTHOR]

Transport properties of pure methane have been calculated in the rigid-rotor approximation using the recently proposed intermolecular potential energy hypersurface [R. Hellmann et al., J. Chem. Phys. 128, 214303 (2008)] and the classical-trajectory method. Results are reported in the dilute-gas limit for the temperature range of 80–1500 K. The calculated thermal conductivity values are in very good agreement with the measured data and correlations. In the temperature range of 310–480 K the calculated values underestimate the best experimental data by 0.5%–1.0%. We suggest that the calculated values are more accurate, especially at low and high temperatures, than the currently available correlations based on the experimental data. Our results also agree well with measurements of thermal transpiration and of the thermomagnetic coefficients. We have shown that although the dominant contribution to the thermomagnetic coefficients comes from the [formula] polarization in the spherical approximation, the contribution of a second polarization, Wj, cannot be neglected nor can a full description of the Wjj polarization. The majority of the volume viscosity measurements around room temperature are consistent with the calculated values but this is not the case at high and low temperatures. However, for nuclear-spin relaxation the calculated values consistently exceed the measurements, which are mutually consistent within a few percent. [ABSTRACT FROM AUTHOR]

Transport properties of pure methane gas have been calculated in the rigid-rotor approximation using the recently proposed intermolecular potential energy hypersurface [R. Hellmann et al., J. Chem. Phys. 128, 214303 (2008)] and the classical-trajectory method. Results are reported in the dilute-gas limit for shear viscosity, viscomagnetic coefficients, and self-diffusion in the temperature range of 80–1500 K. Compared with the best measurements, the calculated viscosity values are about 0.5% too high at room temperature, although the temperature dependence of the calculated values is in very good agreement with experiment between 210 and 390 K. For the shear viscosity, the calculations indicate that the corrections in the second-order approximation and those due to the angular-momentum polarization are small, less than 0.7%, in the temperature range considered. The very good agreement of the calculated values with the experimental viscosity data suggests that the rigid-rotor approximation should be very reasonable for the three properties considered. In general, the agreement for the other measured properties is within the experimental error. [ABSTRACT FROM AUTHOR]

An expression for the viscosity of a dense fluid is presented that includes the effect of molecular shape. The molecules of the fluid are approximated by chains of equal-sized, tangentially jointed, rigid spheres. It is assumed that the collision dynamics in such a fluid can be approximated by instantaneous collisions between two rigid spheres belonging to different chains. The approach is thus analogous to that of Enskog for a fluid consisting of rigid spheres. The description is developed in terms of two molecular parameters, the diameter σ of the spherical segment and the chain length (number of segments) m. It is demonstrated that an analysis of viscosity data of a particular pure fluid alone cannot be used to obtain independently effective values of both σ and m. Nevertheless, the chain lengths of n-alkanes are determined by assuming that the diameter of each rigid sphere making up the chain can be represented by the diameter of a methane molecule. The effective chain lengths of n-alkanes are found to increase linearly with the number C of carbon atoms present. The dependence can be approximated by a simple relationship m=1+(C-1)/3. The same relationship was reported within the context of a statistical associating fluid theory equation of state treatment of the fluid, indicating that both the equilibrium thermodynamic properties and viscosity yield the same value for the chain lengths of n-alkanes. [ABSTRACT FROM AUTHOR]

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 volume viscosity, depolarized Rayleigh scattering, and nuclear spin relaxation for temperatures ranging from 200 to 1000 K. Three recent carbon dioxide potential energy hypersurfaces have been investigated. Calculated values for the rotational collision number for all three intermolecular surfaces are consistent with the measurements and indicate that the temperature dependence of the Brau-Jonkman correlation is not applicable for carbon dioxide. The results for the depolarized Rayleigh scattering cross section and the nuclear spin relaxation cross section show that calculated values for the generally more successful potentials differ from the observations by 9% at about 290 K, although agreement is obtained for nuclear spin relaxation at about 400 K. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

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. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Byline: Hector Jorquera, German Orrego, Julio Castro, Velisa Vesovic This study focused on establishing trends in the period 19882001 in PM2.5, PM10 and ozone concentrations in Santiago, Chile, and linking those to population exposure. There is strong seasonality in the concentration levels, driven by prevailing meteorological conditions, with the concentration of particulates peaking at the beginning of winter, whereas the ozone concentration is highest during the summer. The levels of PM2.5 and PM10 have substantially decreased since the late 1980s and so has the population exposure. Nevertheless, the majority of the population is still exposed to annual average levels that are above standard values. The situation with ozone exposure is different; no substantial decrease can be observed in the data. If anything, certain parts of Santiago, notably the south-east, have shown increased levels of ozone. Overall population exposure indicates that the average person was more at risk of ozone in the year 2000 than they were in 1993.

The behavior of the volume viscosity in atom-molecule gas mixtures is investigated in the framework of the first-order Enskog–Chapman expansion when the internal-energy relaxation cross section for atom-molecule collisions is small compared to that for molecule-molecule collisions. Two phenomena are analyzed: first, the sensitivity of the volume viscosity to this particular cross section allows the volume viscosity of the atom-molecule mixture to be significantly larger than that of the pure molecular gas; second, when this cross section is set to zero, the volume viscosity becomes discontinuous at the pure-atom limit.© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]