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At least 271 records · Page 15

Vaporization thermodynamics of K2S and K2SO3

The vaporization reactions, vapor pressures, and thermodynamics of potassium sulfide and potassium sulfite were studied for purposes of providing fundamental data for the seed cycle in magnetohydrodynamic electric power generation. Rate of effusion studies, supported by tube furnace experiments, X-ray powder diffraction, mass spectrometry and appropriate chemical analyses and tests, revealed that potassium sulfite disproportionates at high temperatures to form potassium sulfide and potassium sulfate. Potassium sulfide was observed to vaporize incongruently, the initial vapors beng predominantly potassium atoms, with minor species being S2 and various K-S molecules. The ratio of K/S2 in the vapor is very large initially and decreases steadily with prolonged heating. Several materials were evaluated for purposes of containing K2S/K2SO3 at temperatures or = 800 C: Pt, Mo, W, quartz, machinable glass, BN, high density graphite, pyrolytic coated graphite, and alumina. Of these, only alumina was observed to be chemically inert to both K2S but reacted with K2SO3. The other materials were not suitable for either substance. Thermodynamic calculations based on measured vapor pressures and approximate free energy functions are described. Results from isothermal total mass loss experiments and from thermogravimetric experiments are also included.

Bennet, J. E.

A proposed approach to the application of nonlinear irreversible thermodynamics to fracture in composite materials

The fracture criteria upon which most fracture mechanics is based involves an energy balance that is not appropriate for the fracture mechanics of viscoelastic materials such as polymer matrix composites. A more appropriate criterion based upon nonequilibrium thermodynamics and involving a power balance rather than an energy balance is proposed. This crierion is based upon a reformulation of the second law of thermodynamics which focuses attention on the total Legendre transform of energy expressed as a functional over time and space. This excess energy functional can be shown to be equivalent to the Rice J integral if the only irreversible process is the propogation of a single crack completely through the thickness of the specimen and if the crack propogation is assured to be independent of time. For the more general case of more than one crack in a viscoelastic medium integration over both time and space is required. Two experimentally measurable parameters are proposed which should permit the evaluation of this more general fracture criterion.

Lindenmeyer, P. H.

Thermodynamics of silicon nitridation - Effect of hydrogen

Equilibrium compositions for the nitridization of Si were calculated to detect the effectiveness of H2 in removal of the oxide film and in increasing the concentration of SiO and reducing the proportions of O2. Gibbs free energy for the formation of SiN2O was computed above 1685 K, and at lower temperatures. The thermodynamic properties of SiN2O2 were then considered from 1000-3000 K, taking into account the known thermodynamic data for 39 molecular combinations of the Si, Ni, and O. The gases formed were assumed ideal mixtures with pure phase condensed species. The mole fractions were obtained for a system of SiO2 with each Si particle covered with a thin layer of SiO2 before nitridation, and a system in which the nitriding atmosphere had access to the Si. The presence of H2 was determined to enhance the removal of NiO2 in the first system, decrease the partial pressure of O2, increase the partial pressures of SiO, Si, H2O, NH3, and SiH4, while its effects were negligible in the Si system.

Shaw, N. J.

Generating Tables of Thermodynamic Properties

Thermodynamic Property Generation program produces tables for any fluid for which state equation, vapor pressure equation, specific heat equation, and critical constants are known. Program calculates thermodynamic properties at any state providing way of obtaining properties at extreme environmental conditions.

Nguyen, S. N.

Lagrange thermodynamic potential and intrinsic variables for He-3 He-4 dilute solutions

For a two-fluid model of dilute solutions of He-3 in liquid He-4, a thermodynamic potential is constructed that provides a Lagrangian for deriving equations of motion by a variational procedure. This Lagrangian is defined for uniform velocity fields as a (negative) Legendre transform of total internal energy, and its primary independent variables, together with their thermodynamic conjugates, are identified. Here, similarities between relations in classical physics and quantum statistical mechanics serve as a guide for developing an alternate expression for this function that reveals its character as the difference between apparent kinetic energy and intrinsic internal energy. When the He-3 concentration in the mixtures tends to zero, this expression reduces to Zilsel's formula for the Lagrangian for pure liquid He-4. An investigation of properties of the intrinsic internal energy leads to the introduction of intrinsic chemical potentials along with other intrinsic variables for the mixtures. Explicit formulas for these variables are derived for a noninteracting elementary excitation model of the fluid. Using these formulas and others also derived from quantum statistical mechanics, another equivalent expression for the Lagrangian is generated.

Jackson, H. W.

Ideal gas thermodynamic properties for the phenyl, phenoxy, and o-biphenyl radicals

Ideal gas thermodynamic properties of the phenyl and o-biphenyl radicals, their deuterated analogs and the phenoxy radical were calculated to 5000 K using estimated vibrational frequencies and structures. The ideal gas thermodynamic properties of benzene, biphenyl, their deuterated analogs and phenyl were also calculated.

Burcat, A.

Theoretical Thermodynamics of Mixtures at High Pressures

The development of an understanding of the chemistry of mixtures of metallic hydrogen and abundant, higher-z material such as oxygen, carbon, etc., is important for understanding of fundamental processes of energy release, differentiation, and development of atmospheric abundances in the Jovian planets. It provides a significant theoretical base for the interpretation of atmospheric elemental abundances to be provided by atmospheric entry probes in coming years. Significant differences are found when non-perturbative approaches such as Thomas-Fermi-Dirac (TFD) theory are used. Mapping of the phase diagrams of such binary mixtures in the pressure range from approx. 10 Mbar to approx. 1000 Mbar, using results from three-dimensional TFD calculations is undertaken. Derivation of a general and flexible thermodynamic model for such binary mixtures in the relevant pressure range was facilitated by the following breakthrough: there exists an accurate nd fairly simple thermodynamic representation of a liquid two-component plasma (TCP) in which the Helmholtz free energy is represented as a suitable linear combination of terms dependent only on density and terms which depend only on the ion coupling parameter. It is found that the crystal energies of mixtures of H-He, H-C, and H-O can be satisfactorily reproduced by the same type of model, except that an effective, density-dependent ionic charge must be used in place of the actual total ionic charge.

Hubbard, W. B.

Hadron thermodynamics in relativistic nuclear collisions

Various phenomenological models based on statistical thermodynamical considerations were used to fit the experimental data at high P sub T to a two temperature distribution. Whether this implies that the two temperatures belong to two different reaction mechanisms, or consequences of Lorentz-contraction factor, or related in a fundamental way to the intrinsic thermodynamics of Space-Time can only be revealed by further theoretical and experimental investigations of high P sub T phenomena in extremely energetic hadron-hadron collisions.

Ammiraju, P.

Predictions of nucleation theory applied to Ehrenfest thermodynamic transitions

A modified nucleation theory is used to determine a critical nucleus size and a critical activation-energy barrier for second-order Ehrenfest thermodynamic transitions as functions of the degree of undercooling, the interfacial energy, the heat-capacity difference, the specific volume of the transformed phase, and the equilibrium transition temperature. The customary approximations of nucleation theory are avoided by expanding the Gibbs free energy in a Maclaurin series and applying analytical thermodynamic expressions to evaluate the expansion coefficients. Nonlinear correction terms for first-order-transition calculations are derived, and numerical results are presented graphically for water and polystyrene as examples of first-order and quasi-second-order transitions, respectively.

Barker, R. E., Jr.

Thermodynamics of clathrate hydrate at low and high pressures with application to the outer solar system

The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.

Lunine, J. I.

Thermodynamic Calculations for Complex Chemical Mixtures

General computer program, CECTRP, developed for calculation of thermodynamic properties of complex mixtures with option to calculate transport properties of these mixtures. Free-energy minimization technique used in equilibrium calculation. Rigorous equations used in transport calculations. Program calculates equilibrium compositions and corresponding thermodynamic and transport properties of mixtures. CECTRP accommodates up to 24 reactants, 20 elements, and 600 products, 400 of which are condensed. Written in FORTRAN IV for any large computer system.

Mcbride, B. J.

Fluid Dynamics and Thermodynamics of Vapor Phase Crystal Growth

The ground-based research effort under this program is concerned with systematic studies of the effects of variations: (1) of the relative importance of buoyancy-driven convection, and (2) of diffusion and viscosity conditions on crystal properties. These experimental studies are supported by thermodynamic characterizations of the systems, based on which fluid dynamic parameters can be determined. The specific materials under investigation include: the GeSe-GeI4, Ge-GeI4, HgTe-HgI2, and Hg sub (1-x)Cd sub (x) Te-HgI2 systems. Mass transport rate studies of the GeSe-GeI system as a function of orientation of the density gradient relative to the gravity vector demonstrated the validity of flux anomalies observed in earlier space experiments. The investigation of the effects of inert gases on mass flux yielded the first experimental evidence for the existence of a boundary layer in closed ampoules. Combined with a thorough thermodynamic analysis, a transport model for diffusive flow including chemical vapor transport, sublimation, and Stefan flow was developed.

Wiedemeier, H.

A study of the applicability of nucleation theory to quasi-thermodynamic transitions of second and higher Ehrenfest-order

The applicability of classical nucleation theory to second (and higher) order thermodynamic transitions in the Ehrenfest sense has been investigated and expressions have been derived upon which the qualitative and quantitative success of the basic approach must ultimately depend. The expressions describe the effect of temperature undercooling, hydrostatic pressure, and tensile stress upon the critical parameters, the critical nucleus size, and critical free energy barrier, for nucleation in a thermodynamic transition of any general order. These expressions are then specialized for the case of first and second order transitions. The expressions for the case of undercooling are then used in conjunction with literature data to estimate values for the critical quantities in a system undergoing a pseudo-second order transition (the glass transition in polystyrene). Methods of estimating the interfacial energy gamma in systems undergoing a first and second order transition are also discussed.

Barker, R. E., Jr.

Space Station Engineering and Technology Development. Proceedings of the Panel on Solar Thermodynamics Research and Technology Development, July 31, 1985

Solar thermodynamics research and technology is reported. Comments on current program activity and future plans with regard to satisfying potential space station electric power generation requirements are provided. The proceedings contain a brief synopsis of the presentations to the panel, including panel comments, and a summary of the panel's observations. Selected presentation material is appended. Onboard maintainability and repair in space research and technology plan, solar thermodynamic research, program performance, onboard U.S. ground based mission control, and technology development rad maps from 10 C to the growth station are addressed.

Source record

The magnetic and thermodynamical structure of a coronal hole

A nonpolytropic model of a polar coronal hole of 2-5 solar radii constructed. The main assumptions are: (1) the magnetic structure of the sun can be described by a combination of dipole-like and radial fields; (2) in the magnetically dominated region rho(nu sq/2) much less than B sq/8 pi the influence of the outflow on the magnetic structure is negligible. The magnetic and thermodynamic structures are obtained by solving the force balance equation for plasma with the observationally derived electron density. Profiles of velocities in the acceleration regime are presented and the influence of the outflow on the thermodynamic structure of the solar corona above the polar region is discussed.

Osherovich, V. A.

Laplace-transform technique for deriving thermodynamic equations from the classical microcanonical ensemble

A direct and convenient method is presented for deriving expressions which equate any thermodynamic state function to averages of specific dynamical functions and their fluctuations over the classical microcanonical distribution. Specific expressions are obtained for a variety of thermodynamic quantities. The effect of various entropy definitions on the results are assessed, and the latter are compared to previous work in the literature. The derived formulas are applied to the analysis of molecular-dynamics computer simulations.

Pearson, E. M.

A study of the applicability of nucleation theory to quasi-thermodynamic transitions of second and higher Ehrenfest-order, supplement 3

The work includes an investigation of the applicability of the nucleation theory to second and higher order thermodynamic transitions in the Ehrenfest sense, and a number of significant conclusions relevant to first order transitions, as well. The underlying theoretical method consisted of expanding the Gibbs' free energy in a Maclarin or Taylor series and then using fundamental thermodynamic determinable quantities, and interpreting the results. Work was performed on the existence and interpretation of an interfacial energy between phases in a second order transition in addition to an investigation of the solid-liquid interfacial energy for various polymers. Extensive considerations were devoted to various aspects of a particular polymer, polyvinylidene fluoride (PVDF or PVF2), including an experimetal investigation of the effects of an applied electric field on the morphology of melt crystallization and on the nucleation and growth of polarized domains.

Barker, R. E., Jr.

Thermodynamic analysis and subscale modeling of space-based orbit transfer vehicle cryogenic propellant resupply

The resupply of the cryogenic propellants is an enabling technology for spacebased orbit transfer vehicles. As part of the NASA Lewis ongoing efforts in microgravity fluid management, thermodynamic analysis and subscale modeling techniques were developed to support an on-orbit test bed for cryogenic fluid management technologies. Analytical results have shown that subscale experimental modeling of liquid resupply can be used to validate analytical models when the appropriate target temperature is selected to relate the model to its prototype system. Further analyses were used to develop a thermodynamic model of the tank chilldown process which is required prior to the no-vent fill operation. These efforts were incorporated into two FORTRAN programs which were used to present preliminary analyticl results.

Defelice, David M.