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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Desorption lifetimes and activation energies influencing gas–surface interactions and multiphase chemical kinetics

Abstract. Adsorption and desorption of gases on liquid or solid substrates are involved in multiphase processes and heterogeneous chemical reactions. The desorption energy (Edes0), which depends on the intermolecular forces between adsorbate and substrate, determines the residence time of chemical species at interfaces. We show how Edes0 and temperature influence the net uptake or release of gas species, the rates of surface–bulk exchange and surface or bulk reactions, and the equilibration timescales of gas–particle partitioning. Using literature data, we derive a parameterization to estimate Edes0 for a wide range of chemical species based on the molecular mass, polarizability, and oxygen-to-carbon ratio of the desorbing species independent of substrate-specific properties, which is possible because of the dominant role of the desorbing species' properties. Correlations between Edes0 and the enthalpies of vaporization and solvation are rooted in molecular interactions. The relation between Edes0 and desorption kinetics reflects the key role of interfacial exchange in multiphase processes. For small molecules and semi-volatile organics (VOC, IVOC, SVOC), Edes0 values around 10–100 kJ mol−1 correspond to desorption lifetimes around nanoseconds to days at room temperature. Even higher values up to years are obtained at low temperatures and for low volatile organic compounds (LVOC, ELVOC/ULVOC) relevant for secondary organic aerosols (SOA). Implications are discussed for SOA formation, gas–particle partitioning, organic phase changes, and indoor surface chemistry. We expect these insights to advance the mechanistic and kinetic understanding of multiphase processes in atmospheric and environmental physical chemistry, aerosol science, materials science, and chemical engineering.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1962

Estimated Viscosities and Thermal Conductivities of Gases at High Temperatures

Viscosities and thermal conductivities, suitable for heat-transfer calculations, were estimated for about 200 gases in the ground state from 100 to 5000 K and 1-atmosphere pressure. Free radicals were included, but excited states and ions were not. Calculations for the transport coefficients were based upon the Lennard-Jones (12-6) potential for all gases. This potential was selected because: (1) It is one of the most realistic models available and (2) intermolecular force constants can be estimated from physical properties or by other techniques when experimental data are not available; such methods for estimating force constants are not as readily available for other potentials. When experimental viscosity data were available, they were used to obtain the force constants; otherwise the constants were estimated. These constants were then used to calculate both the viscosities and thermal conductivities tabulated in this report. For thermal conductivities of polyatomic gases an Eucken-type correction was made to correct for exchange between internal and translational energies. Though this correction may be rather poor at low temperatures, it becomes more satisfactory with increasing temperature. It was not possible to obtain force constants from experimental thermal conductivity data except for the inert atoms, because most conductivity data are available at low temperatures only (200 to 400 K), the temperature range where the Eucken correction is probably most in error. However, if the same set of force constants is used for both viscosity and thermal conductivity, there is a large degree of cancellation of error when these properties are used in heat-transfer equations such as the Dittus-Boelter equation. It is therefore concluded that the properties tabulated in this report are suitable for heat-transfer calculations of gaseous systems.

HEAT TRANSFER↗
NASA NTRS1973

Method for estimating solubility parameter

Semiempirical correlations have been developed between solubility parameters and refractive indices for series of model hydrocarbon compounds and organic polymers. Measurement of intermolecular forces is useful for assessment of material compatibility, glass-transition temperature, and transport properties.

Lawson, D. D.↗
NASA NTRS1974

Correlation of the rate of ultrasound propagation with other characteristic magnitudes of the liquid state

The application of ultrasonic radiation to the procedure for determining the physical properties of liquids is discussed. The basis for linking the kinetic properties of liquids to the equilibrium properties through the molecular structure and the potential of the intermolecular forces is defined. The test procedure using ultrasonic radiation is described. Results of tests with specified fluids are tabulated.

Stetiu, C.↗
NASA NTRS1974

Comment on determination of the interaction potential between Ar and HCl

To test the accuracy of the Gordon-Kim theory of intermolecular forces, predicted and experimental values are compared for Ar-HCl. The method appears to accurately predict the short-range repulsive forces and also the position (but possibly not the depth) of the potential well.

Green, S.↗
NASA NTRS1976

Partition function corrections

The vibration-rotation interaction coupling in diatomic molecules is analyzed and first-order expressions for the energy levels are deduced. Corrections to the partition function to account for this coupling are derived. The effects of long-range intermolecular forces due to induced dipole-induced dipole interactions, dipole-induced dipole interactions, charge-dipole interactions, and charge-charge interactions are considered. London's quantized oscillator model of the induced dipole-induced dipole interaction is developed. The partition function including effects of such dispersion forces is derived and is shown to lead to the virial equation of state. For a model combining the hard sphere and long-range attractive type potentials, this is found to lead to the van der Waals equation of state. The equation of state near the critical point is presented in reduced form (thermodynamic variables expressed in units of critical point values). Finally, approximate corrections to the electronic partition functions are derived to account for perturbations of excited electronic states induced by neighboring neutral particles, heavy ions, and fast electron collisions.

Source record↗
NASA NTRS1976

Rotational excitation of CO by collisions with He, H, and H2 under conditions in interstellar clouds

Cross sections for rotational excitation of small molecules by low-energy collisions with helium and hydrogen can currently be obtained via accurate numerical solution of the quantum equations that describe both intermolecular forces and collision dynamics. The relevant methods are discussed in some detail and applied to compute excitation rates for carbon monoxide. These calculations also predict collision-induced spectral pressure-broadening constants which are in excellent agreement with available experimental data.

Green, S.↗
NASA NTRS1985

Collisional excitation of molecules in dense interstellar clouds

State transitions which permit the identification of the molecular species in dense interstellar clouds are reviewed, along with the techniques used to calculate the transition energies, the database on known molecular transitions and the accuracy of the values. The transition energies cannot be measured directly and therefore must be modeled analytically. Scattering theory is used to determine the intermolecular forces on the basis of quantum mechanics. The nuclear motions can also be modeled with classical mechanics. Sample rate constants are provided for molecular systems known to inhabit dense interstellar clouds. The values serve as a database for interpreting microwave and RF astrophysical data on the transitions undergone by interstellar molecules.

Green, S.↗
NASA NTRS1987

Collisional excitation of an asymmetric rotor, silicon dicarbide

Rotational excitation rates have been computed for the asymmetric top molecule SiC2 in collisions with low-energy He atoms. The intermolecular forces were obtained from an electron gas model, and collision dynamics were treated within the infinite-order sudden approximation. Total excitation rates, i.e., summed over final levels, are expected to be accurate to about 50 percent, and the larger state-to-state rates are likely to be within a factor of about 2 of the correct values, although some of the smaller (and less important) rates may be less accurate. These rates are also thought to reflect, within this level of accuracy, rates for excitation by collisions with H2 molecules.

Palma, Amedeo↗
NASA NTRS1987

Collisional excitation of interstellar sulfur dioxide

State-to-state rotational excitation rates for the asymmetric top molecule SO2 in collisions with low-energy He atoms have been computed. The intermolecular forces were obtained from an electron gas model, and collision dynamics were treated with the finite-order sudden approximation. The total excitation rate is probably accurate to better than 50 percent; however, individual state-to-state rates may be in error by factors of 2 or 3, and some smaller rates may be accurate only to an order of magnitude. Present results are expected to reflect within the same level of accuracy rates for excitation by collisions with H2 molecules.

Palma, Amedeo↗
NASA NTRS1987

Collisional excitation of interstellar cyclopropenylidene

Theoretical rotational excitation rates were computed for C3H2 in collisions with He atoms at temperatures from 30 to 120 K. The intermolecular forces were obtained from accurate self-consistent field and perturbation theory calculations, and collision dynamics were treated within the infinite-order sudden approximation. The accuracy of the latter was examined by comparing with the more exact coupled states approximation.

Green, Sheldon↗
NASA NTRS1989

Structures of cyano-biphenyl liquid crystals

The structures of p-alkyl- p'-cyano- bicyclohexanes, C(n)H(2n+1) (C6H10)(C6H10) CN (n-CCH), and p-alkyl- p'-cyano- biphenyls, C(n)H(2n+1) (C6H4)(C6H4) CN (n-CBP), were studied. It is convenient to use an x ray image intensification device to search for symmetric x ray diffraction patterns. Despite the similarities in molecular structures of these compounds, very different crystal structures were found. For the smectic phase of 2CCH, the structure is close to rhombohedral with threefold symmetry. In contrast, the structure is close to hexagonal close-packed with two molecules per unit cell for 4CCH. Since intermolecular forces may be quite weak for these liquid crystals systems, it appears that crystal structures change considerably when the alkyl chain length is slightly altered. Different structures were also found in the crystalline phase of n-CBP for n = 6 to 9. For n = 7 to 9, the structures are close to monclinic. The structures are reminiscent of the smectic-A liquid crystal structures with the linear molecules slightly tilted away from the c-axis. In contrast, the structure is quite different for n = 6 with the molecules nearly perpendicular to the c-axis.

Chu, Yuan-Chao↗
NASA NTRS1992

Dissociation energy of molecules in dense gases

A general approach is presented for calculating the reduction of the dissociation energy of diatomic molecules immersed in a dense (n = less than 10 exp 22/cu cm) gas of molecules and atoms. The dissociation energy of a molecule in a dense gas differs from that of the molecule in vacuum because the intermolecular forces change the intramolecular dynamics of the molecule, and, consequently, the energy of the molecular bond.

Kunc, J. A.↗
NASA NTRS1992

Boundary layer study on nozzle wall at hypersonic velocities

The boundary layer on the wall of the Hypervelocity Tunnel 9 was investigated with pitot pressure and total temperature measurements. Experimental results are presented for standard and supercooled Mach 14 runs. The boundary layer data at supercooled conditions are compared to numerical predictions made with a Navier-Stokes algorithm including vibrational nonequilibrium and intermolecular force effects. For standard tunnel conditions, the numerical solutions agree well with experimental data. For the supercooled cases, the numerical code predicts the total temperature but overpredicts the pitot pressure.

Jones, Kenneth M.↗
NASA NTRS1959

One-dimensional flows of an imperfect diatomic gas

With the assumptions that Berthelot's equation of state accounts for molecular size and intermolecular force effects, and that changes in the vibrational heat capacities are given by a Planck term, expressions are developed for analyzing one-dimensional flows of a diatomic gas. The special cases of flow through normal and oblique shocks in free air at sea level are investigated. It is found that up to a Mach number 10 pressure ratio across a normal shock differs by less than 6 percent from its ideal gas value; whereas at Mach numbers above 4 the temperature rise is considerable below and hence the density rise is well above that predicted assuming ideal gas behavior. It is further shown that only the caloric imperfection in air has an appreciable effect on the pressures developed in the shock process considered. The effects of gaseous imperfections on oblique shock-flows are studied from the standpoint of their influence on the life and pressure drag of a flat plate operating at Mach numbers of 10 and 20. The influence is found to be small. (author)

Source record↗
NASA NTRS1993

Marangoni effect induced convection in material processing under microgravity (M-18)

On the ground the upper layer of the liquid in a vessel heated from below becomes hotter than the lower layer. This well-known phenomenon results from buoyancy-induced convection. Though this means that the buoyancy-induced convection is not dominant under microgravity conditions in space, another convection called Marangoni convection may possibly occur. This convection results from an intermolecular force which acts on a free surface, that is surface tension. Since it is stronger at lower temperatures, the liquid surface near the heated wall is pulled to the cooled side as shown. This surface movement causes the inner convection. Marangoni convection, however, may be negligible on the Earth, for the molecular force is generally smaller than buoyancy. Various tests on material processing were recently conducted in space and some high quality crystals free from buoyancy convection were obtained. But, at the same time, others proved to be less uniform than expected in the components' distribution. This nonuniformity seems to be mainly caused by Marangoni convection. It is, therefore, very important to know how to control the convection by studying its characteristics, but the problem is that on the ground it is impossible to carry out the experiment without gravity. That is what a space experiment aboard the space shuttle is planned as the First Material Processing Tests (FMPT) of Japan. The experiment on Marangoni flow visualization is being performed in order to investigate the characteristics of convection in uni-dimensional melt growth under microgravity conditions.

Enya, S.↗
NASA NTRS1994

Theoretical studies of a molecular beam generator

At present no adequate computer code exists for predicting the effects of thermal nonequilibrium on the flow quality of a converging-diverging N2 nozzle. It is the purpose of this research to develop such a code and then perform parametric studies to determine the effects of intermolecular forces (high gas pressure) and thermal nonequilibrium (the splitting of temperature into a vibrational and rotational-translational excitation) upon the flow quality. The two models to be compared are given. Appendix A contains nomenclature and additional relationships.

Heinbockel, John↗