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NASA NTRS1974

Ground-state energies of simple metals

A structural expansion for the static ground-state energy of a simple metal is derived. Two methods are presented, one an approach based on single-particle band structure which treats the electron gas as a nonlinear dielectric, the other a more general many-particle analysis using finite-temperature perturbation theory. The two methods are compared, and it is shown in detail how band-structure effects, Fermi-surface distortions, and chemical-potential shifts affect the total energy. These are of special interest in corrections to the total energy beyond third order in the electron-ion interaction and hence to systems where differences in energies for various crystal structures are exceptionally small. Preliminary calculations using these methods for the zero-temperature thermodynamic functions of atomic hydrogen are reported.

Hammerberg, J.↗

NASA NTRS1974

Degeneracy effects of neutrino mass ejection in supernovae

A neutrino mechanism is discussed in order to explain supernovae in massive stars. An argument is presented for supernova mass ejection through leptonic neutrino transport characteristics suppressed by the arbitrary zero chemical potential condition. Results show that lepton conservation effects may be important in supernova neutrino transport. At low temperature and density the diffusion approximation becomes less precise because of the long mean free paths of low energy neutrinos. The amount of equilibrium neutrino spectrum affected here is small over most of the collapsing supernova structure.

Mazurek, T. J.↗

NASA NTRS1975

Thermal energy storage

The principles involved in thermal energy storage by sensible heat, chemical potential energy, and latent heat of fusion are examined for the purpose of evolving selection criteria for material candidates in the low ( 0 C) and high ( 100 C) temperature ranges. The examination identifies some unresolved theoretical considerations and permits a preliminary formulation of an energy storage theory. A number of candidates in the low and high temperature ranges are presented along with a rating of candidates or potential candidates. A few interesting candidates in the 0 to 100 C region are also included. It is concluded that storage by means of reactions whose reversibility can be controlled either by product removal or by catalytic means appear to offer appreciable advantages over storage with reactions whose reversability cannot be controlled. Among such advantages are listed higher heat storage capacities and more favorable options regarding temperatures of collection, storage, and delivery. Among the disadvantages are lower storage efficiencies.

Grodzka, P. G.↗

NASA NTRS1979

High temperature electrolytic recovery of oxygen from gaseous effluents from the carbo-chlorination of lunar anorthite and the hydrogenation of ilmenite: A theoretical study

A thermodynamic analysis discusses the compositions of gaseous effluents from the reaction of carbon and chlorine and of hydrogen with lunar anorthite and ilmenite, respectively. The computations consider the effects of the indigenous volatiles on the solid/gas reactions and on the composition of the effluent gases. A theoretical parameterization of the high temperature electrolysis of such gases is given for several types of solid ceramic electrolytes, and the effect of oxygen removal on the effluents is computed. Potential chemical interactions between the gases and the ceramic electrolytes are analyzed and discussed.

Erstfield, T. E.↗

NASA NTRS1979

Thermodynamics of selected trace elements in the Jovian atmosphere

The thermochemistry of several hundred compounds of twelve selected trace elements (Ge, Se, Ga, As, Te, Pb, Sn, Cd, Sb, Tl, In, and Bi) has been investigated for solar composition material along a Jupiter adiabat. The results indicate that AsF3, InBr, TlI, and SbS, in addition to CO, PH3, GeH4, AsH3, H2Se, HCl, HF, and H3BO3 proposed by Barshay and Lewis (1978), may be potential chemical tracers of atmospheric dynamics. The reported observation of GeH4 is interpreted on the basis of new calculations as implying rapid vertical transport from levels where the temperature is greater than or equal to 800 K. Upper limits are also set on the abundances of many gaseous compounds of the elements investigated.

Fegley, B., Jr.↗

NASA NTRS1981

On the theory of Gamma Ray Amplification through Stimulated Annihilation Radiation (GRASAR)

The theory of photon emission, absorption, and scattering in a relativistic plasma of positrons, electrons, and photon was studied. Expressions for the emissivities and absorption coefficients of pair annihilation, pair production, and Compton scattering are given and evaluated numerically. The conditions for negative absorption were investigated. In a system of photons and e(+) - e(-) pairs, an emission line at at approximately 0.43 MeV can be produced by grasar action provided that the pair chemical potential exceeds approximately 1 MeV. At a temperature of approximately 10 to the 9th power. This requires a pair density approximately 10 to the 30th power cm to the (-3) power a value much larger than the thermodynamic equilbrium pair density at this temperature. This emission line could account without a gravitational redshift for the observed lines at this energy from gamma ray bursts.

Ramaty, R.↗

NASA NTRS1982

Functional membranes. Present and future

The present situation and the future development of the functional membrane are discussed. It is expected that functional membranes will play increasingly greater roles in the chemical industry of the coming decade. These membranes are formed from polymer films, liquid membranes or bilayer membranes. The two most important technologies based on the polymeric membrane are reverse osmosis and ion exchange. The liquid membrane is used for separation of ionic species; an extension of the solvent extraction process. By using appropriate ligands and ionophores, highly selective separations are realized. The active transport is made possible if the physical and chemical potentials are applied to the transport process. More advanced functional membranes may be designed on the basis of the synthetic bilayer membrane.

Kunitake, T.↗

NASA NTRS1982

Statistical mechanics of dilute liquid mixtures of He3 in He4

The Woo-Tan-Massey quantum-mechanical theory of dilute mixtures of He-3 in liquid He-4 is extended to incorporate superfluid flow. Then statistical-mechanical principles are employed to find explicit formulas for thermodyanmic and hydrodynamic properties of mixtures, such as internal energy, free energy, entropy, pressure, chemical potential, and normal-fluid and superfluid densities. This paper is the first in a planned series that applies methods originally developed for pure liquid He-4 to dilute mixtures as a means of establishing a comprehensive theory that includes a theoretical bridge between a microscopic description of the mixtures and a hydrodynamic two-fluid model. Ultimately effects of applied electric and magnetic fields on dilute solutions are also planned to be treated.

Jackson, H. W.↗

NASA NTRS1982

Nucleation theory - Is replacement free energy needed?

It has been suggested that the classical theory of nucleation of liquid from its vapor as developed by Volmer and Weber (1926) needs modification with a factor referred to as the replacement free energy and that the capillary approximation underlying the classical theory is in error. Here, the classical nucleation equation is derived from fluctuation theory, Gibb's result for the reversible work to form a critical nucleus, and the rate of collision of gas molecules with a surface. The capillary approximation is not used in the derivation. The chemical potential of small drops is then considered, and it is shown that the capillary approximation can be derived from thermodynamic equations. The results show that no corrections to Volmer's equation are needed.

Doremus, R. H.↗

NASA NTRS1982

Design principles for high efficiency small-grain polysilicon solar cells, with supporting experimental studies

Design principles suggested here aim toward high conversion efficiency (greater than 15 percent) in polysilicon cells. The principles seek to decrease the liabilities of both intragranular and grain-boundary-surface defects. The advantages of a phosphorus atom concentration gradient in a thin (less than 50 microns) base of a p(+)/n(x)/n(+) drift-field solar cell, which produces favorable gradients in chemical potential, minority-carrier mobility and diffusivity, and recombination lifetime (via phosphorus gettering) are suggested. The degrading effects of grain boundaries are reduced by these three gradients and by substituting atoms (P, H, F or Li) for vacancies on the grain-boundary surface. From recent experiments comes support for the benefits of P diffusion down grain boundaries and, for quasi-grain-boundary-free and related structures. New analytic solutions for the n(x)-base include the effect of a power-law dependence between P concentration and lifetime. These provide an upper-bound estimate on the open circuit voltage. Finite-difference numerical solutions of the six Shockley equations furnish complete information about all solar-cell parameters and add insight concerning design.

Lindholm, F. A.↗

NASA NTRS1987

Utilization of FEP energetics

The research and development work on Fountain Effect Pump Systems (FEP systems) has been of interest in the competition between mechanical pumps for He II and FEP units. The latter do not have moving parts. In the course of the work, the energetics have been addressed using one part of a simple four-changes-of-state cycle. One option is the FEP ideal change of state at constant chemical potential (mu). The other option is the two-state sequence mu-P with a d mu=0 state change followed by an isobar. Questions of pump behavior, of flow rate response to temperature difference at the hot end, and related questions of thermodynamic cycle completion and heat transfer have been addressed. Porous media data obtained elucidate differences between vapor-liquid phase separation (VLPS) and Zero Net Mass Transfer (ZNMF).

Frederking, T. H. K.↗

NASA NTRS1988

A calorimetric determination of the enthalpy of formation and a description of the defect structure of the ordered beta-phase /Ni, Cu/ /1-x/ Al/x/

In order to describe thermodynamically the defect structure of an ordered B-Hume-Rothery phase, the heat of formation of (Ni,Cu)(1-x)Al(x) was measured at 1100 K as a function of concentration in the range x (sub Al) = 0.4 and 0.55 for three substitution rations x (sub Ni)/x (sub Cu) = infinity; 11; 5. The heat of formation of the NiAl beta-phase is strongly negative. For the stoichiometric composition it is -72.2 kJ/g-atom. On both the nickel-rich side and the aluminum-rich side the magnitude of the enthalpy of formation decreases linearly with concentration. Substitution of nickel for copper decreases the magnitude of the enthalpy of formation over the entire homogeneity range for the phase (Ni,Cu)(1-x)Al(x). The curve for the enthalpy of formation as well as the literature values for the chemical potential of aluminum are described with great accuracy by the disorder model of Wagner-Schottky.

Henig, E. T.↗

NASA NTRS1988

Two puzzling aspects of protein crystal growth

A study is presented of several mechanisms which may reduce crystal growth rates and or terminate crystal growth. It is found that salt gradients which change the local chemical potential of the protein are insufficient to account for the slow crystal growth rates which have been reported. Contaminants which adsorb protein from solution may reduce the effective protein concentration, but the impurity's concentration and its affinity for protein are unknown. Association of protein molecules in bulk solution can reduce the monomer concentration significantly, but extant theory and experiment are not sensitive enough to determine the actual concentration of aggregates in solution. For systems of interest, shear-induced effects were found to be too weak to interfere with normal binding of incoming protein molecules. Although we found that most crystal growth occurs in a regime where both interfacial kinetics and diffusion influence crystal growth, the role of mass transfer rates on the terminal size of crystals is unknown, primarily because no data exist which cover the size range of interest (0.1 mm to 1 mm in length).

Grant, M. L.↗

NASA NTRS1988

Continental crustal formation and recycling: Evidence from oceanic basalts

Despite the wealth of geochemical data for subduction-related magma types, and the clear importance of such magmas in the creation of continental crust, there is still no concensus about the relative magnitudes of crustal creation versus crustal destruction (i.e., recycling of crust into the mantle). The role of subducted sediment in the formation of the arc magmas is now well documented; but what proportion of sediment is taken into the deeper mantle? Integrated isotopic and trace element studies of magmas erupted far from presently active subduction zones, in particular basaltic rocks erupted in the ocean basins, are providing important information about the role of crustal recycling. By identifying potential chemical tracers, it is impossible to monitor the effects of crustal recycling, and produce models predicting the mass of material recycled into the mantle throughout long periods of geological time.

Saunders, A. D.↗

NASA NTRS1990

Early results from the Cosmic Background Explorer (COBE)

The Cosmic Background Explorer, launched 18 Nov. 1989, has nearly completed its first full mapping of the sky with all three of its instruments: A Far Infrared Absolute Spectrometer (FIRAS) covering 0.1 to 10 mm, a set of Differential Microwave Radiometers (DMR) operating at 3.3, 5.7, and 9.6 mm, and a diffuse Infrared Background Experiment (DIRBE) spanning 1 to 300 microns in ten bands. A preliminary map of the sky derived from DIRBE data is presented. Initial cosmological implications include: a limit on the comptonization parameter of 0.001, on the chemical potential parameter of 0.01, a strong limit on the existence of a hot smooth intergalactic medium, and a confirmation that the dipole anisotropy has the spectrum expected from a Doppler shift of a blackbody. There are no significant anisotropies in the microwave sky detected, other than from our own galaxy and a cos theta dipole anisotropy whose amplitude and direction agree with previous data. At shorter wavelengths, the sky spectrum and anisotropies are dominated by emission from local sources of emission within our Galaxy and Solar System. Preliminary comparison of IRAS (Infrared Astronomical Satellite) and DRIBE sky brightnesses toward the ecliptic poles shows the IRAS values to be significantly higher than found by DRIBE at 100 microns. The presence of gain and zero point errors in the IRAS total brightness data is suggested. The spacecraft, instrument designs, and data reduction methods are described.

Mather, J. C.↗

NASA NTRS1991

Middle atmosphere heating by exothermic chemical reactions involving odd-hydrogen species

The rate of heating which occurs in the middle atmosphere due to four exothermic reactions involving members of the odd-hydrogen family is calculated. The following reactions are considered: O + OH yields O2 + H; H + O2 + M yields HO2 + M; H + O3 yields OH + O2; and O + HO2 yields OH + O2. It is shown that the heating rates due to these reactions rival the oxygen-related heating rates conventionally considered in middle-atmosphere models. The conversion of chemical potential energy into molecular translational energy (heat) by these odd-hydrogen reactions is shown to be a significant energy source in the middle atmosphere that has not been previously considered.

Mlynczak, Martin G.↗

NASA NTRS1991

Early results from the Cosmic Background Explorer (COBE)

Data obtained with the FIR Absolute Spectrophotometer, Differential Microwave Radiometers, and Diffuse IR Background Experiment (DIRBE) on the COBE satellite since its launch in November 1989 are briefly characterized. The COBE spacecraft and its 900-km 99-deg orbit are described; the scientific goals and capabilities of the instruments are reviewed; and sample DIRBE data are presented in a map and graph. Upper limits on the Comptonization parameter (y less than 0.001) and the chemical potential (mu less than 0.01 at the 3sigma level) are determined, and the spectrum of the dipole anisotropy is shown to be that of a Doppler-shifted blackbody. The DIRBE 100-micron sky brightness values at the ecliptic poles are found to be significantly lower than those measured by IRAS.

Mather, J. C.↗

NASA NTRS1991

Nonlocal thermodynamic equilibrium processes in ozone - Implications for the energy budget of the mesosphere and lower thermosphere

The conversion of chemical potential energy and infrared radiative energy to kinetic energy by non-LTE processes involving ozone is a potentially significant source of heat in the terrestrial upper mesosphere and lower thermosphere. Heating rates are calculated and compared using two different statistical equilibrium models previously applied in the analysis of measurements of limb emission from ozone. The calculated heating depends strongly on the assumed distribution and relaxation of energy in the quasi-nascent ozone molecule. Finally, in the absence of a detailed data base of rate coefficients it may be possible to estimate the heating rate due to non-LTE processes in ozone from appropriate satellite measurements of the ozone concentration and of the infrared emission from ozone in the 9-12 micron spectral interval.

Milynczak, Martin G.↗