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At least 19 records

Disequilibrium condensation environments in space - A frontier in thermodynamics

The thermal-disequilibrium aspect of the problem of dust-particle formation from a gas phase in an open space environment is discussed in an effort to draw attention to the space condensation environment as an interesting arena for application and extension of the ideas and formalisms of nonequilibrium thermodynamics. It is shown that quasi-steady states with a disequilibrium between the gas-phase kinetic temperature and the condensed-phase internal temperature appear to be the norm of condensation environments in space. Consideration of the case of condensation onto a bulk condensed phase indicates that these quasi-steady states may constitute Prigogine dissipative structures. It is suggested that a proper study of the process of condensation in a space environment should include any effects arising from thermal disequilibrium.

De, B. R.↗

On the comparison between equilibrium and disequilibrium condensation sequences of meteorites

A definition is presented of a simple formalism for calculating the condensation sequence of meteoritic minerals in a cooling vapor phase in temperature disequilibrium (between the vapor phase and the condensed phase) when such minerals condense congruently. Certain preliminary comments are made about the possibility of judging the relative plausibility of the equilibrium and the disequilibrium models from the observations in meteorites if a monotonic cooling were indeed the course of condensation in either case.

De, B. R.↗

Chemical evolution of the Earth: Equilibrium or disequilibrium process?

To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

Sato, M.↗

Vertical distribution of disequilibrium species in Jupiter's troposphere

Sources of organic matter and inorganic tracers on Jupiter, including solar UV photolysis, lightning discharges, and convective quenching of hot gases from the lower atmosphere, are reviewed in light of earth-based and Voyager data with the purpose of predicting the tropospheric steady-state abundances and vertical distributions of HCN, CH2O, and other species. It is concluded that a steady-state mole fraction of HCN in the Jovian troposphere of only about 10 to the -12th could be maintained by vertical transport of hot gases from the deep atmosphere. The observed HCN abundance, roughly X(HCN) = 10 to the -9th, appears to be due to photochemical reactions. After HCN, the most abundant organic-disequilibrium species in the troposphere is probably C2H6, derived from direct photolysis of CH4 at high altitudes, with a mole fraction of about 10 to the -10th at the H2O cloud level. Inorganic tracers of disequilibrium processes are also briefly summarized.

Lewis, J. S.↗

Th-230 - U-238 series disequilibrium of the Olkaria rhyolites Gregory Rift Valley, Kenya: Residence times

U-series disequilibrium analyses have been conducted on samples from Olkaria rhyolite centers with ages being available for all but one center using both internal and whole rock isochrons. 67 percent of the rhyolites analyzed show U-Th disequilibrium, ranging from 27 percent excess thorium to 36 percent excess uranium. Internal and whole rock isochrons give crystallization/formation ages between 65 ka and 9 ka, in every case these are substantially older than the eruptive dates. The residence times of the rhyolites (U-Th age minus the eruption date) have decreased almost linearly with time, from 45 ka to 7 Ka suggesting a possible increase of activity within the system related to increased basaltic input. The long residence times are mirrored by large Rn-222 fluxes from the centers which cannot be explained by larger U contents.

Black, S.↗

Equilibrium and disequilibrium chemistry of adiabatic, solar-composition planetary atmospheres

The impact of atmospheric and cloud-structure models on the nonequilibrium chemical behavior of the atmospheres of the Jovian planets is discussed. Quantitative constraints on photochemical, lightning, and charged-particle production of organic matter and chromophores are emphasized whenever available. These considerations imply that inorganic chromophore production is far more important than that of organic chromophores, and that lightning is probably a negligibly significant process relative to photochemistry on Jupiter. Production of complex molecules by gas-phase disequilibrium processes on Saturn, Uranus, and Neptune is severely limited by condensation of even simple intermediates.

Lewis, J. S.↗

Vibrational disequilibrium in low pressure clouds

Steady state vibrational populations of SiO and CO in several dilute blackbody radiation fields have been calculated as a function of total pressure, kinetic temperature, and chemical composition of the gas. An approximate calculation for polyatomic molecules has also been carried out. Vibrational disequilibrium becomes increasingly significant as the total pressure and radiation density decrease. Many regions of postulated grain formation are found to be far out of thermal equilibrium before the onset of condensation. The use of classical nucleation theory and equilibrium thermodynamics to predict the onset of condensation and the composition of the solids or the molecular composition of the gas phase in such regions therefore is very questionable and needs to be examined for each case.

Nuth, J. A.↗

Evidence for disequilibrium of ortho and para hydrogen on Jupiter from Voyager IRIS measurements

Preliminary results of an analysis of the ortho state/para state ratio (parallel/antiparallel) for molecular H2 in the Jovian atmosphere using Voyager IR spectrometer (IRIS) data are reported. The study was undertaken to expand the understanding of the thermodynamics of a predominantly H2 atmosphere, which takes about 100 million sec to reach equilibrium. IRIS data provided 4.3/cm resolution in the 300-700/cm spectral range dominated by H2 lines. Approximately 600 spectra were examined to detect any disequilibrium between the hydrogen species. The results indicate that the ortho-para ratio is not in an equilibrium state in the upper Jovian troposphere. A thorough mapping of the para-state molecules in the upper atmosphere could therefore aid in mapping the atmospheric flowfield.

Conrath, B. J.↗

Heat transfer to two-phase air/water mixtures flowing in small tubes with inlet disequilibrium

The cooling of gas turbine components was the subject of considerable research. The problem is difficult because the available coolant, compressor bleed air, is itself quite hot and has relatively poor thermophysical properties for a coolant. Injecting liquid water to evaporatively cool the air prior to its contact with the hot components was proposed and studied, particularly as a method of cooling for contingency power applications. Injection of a small quantity of cold liquid water into a relatively hot coolant air stream such that evaporation of the liquid is still in process when the coolant contacts the hot component was studied. No approach was found whereby heat transfer characteristics could be confidently predicted for such a case based solely on prior studies. It was not clear whether disequilibrium between phases at the inlet to the hot component section would improve cooling relative to that obtained where equilibrium was established prior to contact with the hot surface.

Janssen, J. M.↗

Small-scale disequilibrium in a magmatic inclusion and its more silicic host

An investigation of small-scale isotopic, compositional, and mineralogical variation across the interface of a basaltic-andesite inclusion and its dacitic host from Cerro-Chascon, a Holocene dome in northern Chile, is discussed. Serial sectioning across the interface of the inclusion and its host dacite, complemented by microdrill sampling and detailed microprobe work, has enabled an examination of the scale of mixing and chemical disequilibrium. The composition of the inclusion is found to be relatively homogeneous; the dacite host is heterogeneous on a small scale; the isotopic composition in the marginal zone shows the highest Sr-87/Sr-86 and lowest Nd-143/Nd-144; the large plagioclase crystals in the inclusions and host are xenocrystic. These differences are reconciled with a model of magma evolution in a crustal magma chamber.

Davidson, Jon P.↗

Th-230 - U-238 series disequilibrium of the Olkaria basalts Gregory Rift Valley, Kenya

U-Th disequilibrium analyses of the Naivasha basalts show a very small (U-238/Th-230) ratios which are lower than any previously analyzed basalts. The broadly positive internal isochron trend from one sample indicates that the basalts may have source heterogeneities, this is supported by earlier work. The Naivasha complex comprises a bimodal suite of basalts and rhyolites. The basalts are divided into two stratigraphic groups each of a transitional nature. The early basalt series (EBS) which were erupted prior to the Group 1 comendites and, the late basalt series (LBS) which erupted temporally between the Broad Acres and the Ololbutot centers. The basalts represent a very small percentage of the overall eruptive volume of material at Naivasha (less than 2 percent). The analyzed samples come from four stratigraphic units in close proximity around Ndabibi, Hell's Gate and Akira areas. The earliest units occur as vesicular flows from the Ndabibi plain. These basalts are olivine-plagioclase phyric with the associated hawaiites being sparsely plagioclase phyric. An absolute age of 0.5Ma was estimated for these basalts. The next youngest basalts flows occur as younger tuft cones in the Ndabibi area and are mainly olivine-plagioclase-clinopyroxcene phyric with one purely plagioclase phyric sample. The final phase of activity at Ndabibi resulted in much younger tuft cones consisting of air fall ashes and lapilli tufts. Many of these contain resorbed plagioclase phenocrysts with sample number 120c also being clinopyroxene phyric. The isotopic evidence for the basalt formation is summarized.

Black, S.↗

Nitrogen and xenon isotopic disequilibrium in Bachmut (L6) chondrule J2689 and matrix

Chondrule J2689, a large (8-mm) RP chondrule from Bachmut (L6) was previously found to be in disequilibrium with its host in a variety of features: (1) It has a fine-grained hornfelsic texture; (2) it contains low amounts of metal with a low-Ni taenite composition not found in the matrix; (3) the Ni/Co ratio of that metal is close to the solar ratio, which is equal to the bulk Ni/Co ratio (23) of the chondrule; (4) the bulk alkali content of the chondrule is high and the Na/K ratio is fractionated with respect to the average L chondrite ratio of 8; (5) Cr is depleted in spite of the high pyroxene content; (6) the siderophile elements are strongly depleted but are fractionated with their abundances increasing with volatility; and (7) the O isotopes of the chondrule and the host are out of equilibrium. However, the (Fe,Mg) silicates, feldspar, and chromite have chemical compositions indistinguishable from that of the host chondrite. We have studied a chip of the chondrite and of adjacent matrix by stepwise heating and by combustion in O for N and Xe isotopic abundances. (1) The chondrule preserved distinct bulk, metal, and O isotopic compositional features. It is therefore unlikely that the 'equilibration' of the major silicates Fe/Mg ratios could have taken place after accretion; (2) the chondrule was well equilibrated before break-up and exposure to cosmic rays; (3) two N signatures in the matrix also indicate that the matrix is not equilibrated; and (4) all data collected so far point toward the presence of unequilibrated Bachmut components. Very few reactions took place after accretion.

Kim, Y.↗

Nucleon-Alpha Particle Disequilibrium and Short-Lived r-Process Radioactivities

r-Process yields can be extremely sensitive to expansion parameters when a persistent disequilibrium between free nucleons and alpha particles is present. This may provide a natural scenario for understanding the variation of heavy and light r-process isotopes in different r-process events. Additional information is contained in the original extended abstract.

Meyer, B. S.↗

Particle excitation, airglow and H2 vibrational disequilibrium in the atmosphere of Jupiter

The extreme ultraviolet EUV emission produced by particle excitation of the hydrogen atmospheres of Jupiter and Saturn is examined using model calculations to determine the nature of the energy deposition process and the effect of such processes on atmospheric structure. Tasks ranging from examination of phenomenologically related processes on Saturn and Titan to analysis of experimental laboratory data required to allow accurate modeling of emissions from hydrogenic atmospheres are investigated. An explanation of the hydrogen H Ly(alpha) bulge in Jupiter's emission from the equatorial region is presented. It is proposed that Saturn, rather then Titan is the major source of the extended hydrogen cloud. The atomic hydrogen detected at the rings of Saturn may originate predominantly from the same source. A cross calibration is obtained between the Pioneer 10 EUV photometer and the Voyager EUV spectrometers, thus providing a direct measure of the temporal morphology of Jupiter between a minimum and a maximum in solar activity. Atomic and molecular data required for the research program are analyzed. An extrapolation of conditions in the upper atmospheres of Jupiter and Saturn produces a predicted condition at Uranus in terms of excitation and hydrogen escape rates that may be observed at Voyager-Uranus encounter.

Shemansky, D. E.↗

Thermal disequilibrium at the top of volcanic clouds and its effect on estimates of the column height

Satellite images of large volcanic explosions reveal that the tops of volcanic eruptions columns are much cooler than the surrounding atmosphere. It is proposed that this effect occurs whenever a mixture of hot volcanic ash and entrained air ascends sufficiently high into a stably stratified atmosphere. Although the mixture is initially very hot, it expands and cools as the ambient pressure decreases. It is shown that cloud-top undercoolings in excess of 20 C may develop in clouds that penetrate the stratosphere, and it is predicted that, for a given cloud-top temperature, variations in the initial temperature of 100-200 C may correspond to variations in the column height of 5-10 km. It is deduced that the present practice of converting satellite-based measurements of the temperature at the top of volcanic eruptions columns to estimates of the column height will produce rather inaccurate results and should therefore be discontinued.

Woods, Andrew W.↗

Th-230 - U-238 series disequilibrium of the Olkaria basalts Gregory Rift Valley, Kenya: Petrogenesis

Strong mixing trends on a (Th-230/Th-232) versus Th diagram show that the basalts are mixed magmas which have undergone interaction with the crust. Instantaneous Th/U ratios are less than time integrated ones but these exceed the Th/U ratios in the MORB and OIB sources. This indicates that the mantle may have undergone some metasomatic fluxing, crustal contamination of the basalts will also enhance these ratios. Early activity on the Akira plain is represented by early basalts and hawaiites. The early basalt samples are known to predate the earliest comendites. The most recent phase of activity is represented by another cinder cone 40-50 m high being feldspar and clinopyroxene phyric. Inclusions which occur in the comendites vary in size and distribution. The largest and most porphyritic are the trachytes (up to 40 cm) with alkali feldspar phases up to 6 mm and small pyroxenes in the ground mass. The second set of inclusions are smaller (up to 10 cm) and are largely aphyric. The distribution of the inclusions are not uniform, the Broad Acres (C5) lavas contain 2-5 percent. The size of the inclusions decrease from south to north, as does the abundance of the trachytic inclusions. The major element variations in the Naivasha basalts, hawaiites and magmatic inclusions are discussed.

Black, S.↗

Th-230 - U-238 series disequilibrium of the Olkaria rhyolites Gregory Rift Valley, Kenya: Petrogenesis

Positive correlations of (U-238/Th-230) versus Th show the rhyolites to be products of partial melting. Positive correlations of U and Cl and U and F show that the U enrichment in the rhyolites is associated with the halogen contents which may be related to the minor phenocryst phase fractionation. Instantaneous Th/U ratios exceed time integrated Th/U ratios providing further evidence of the hydrous nature of the Olkaria rhyolite source. Excess (U-238/Th-230) in the subduction related rocks has been associated to the preferential incorporation of uranium in slab derived fluids, but no evaluation of the size of this flux has been made. The majority of the Naivasha samples show a (U-238/Th-230) less than 1 and plot close to the subduction related samples indicating the Naivasha rhyolites may also have been influenced by fluids during their formation. In general samples with high (U-238/Th-230) ratios reflecting recent enrichment of uranium relative to thorium have high thorium contents, thereby the high (U-238/Th-230) ratios are restricted to the most incompatible element enriched magmas and, hence, are a good indication that the rhyolites were formed by partial melting. If a fluid phase had some influence on the formation of the rhyolites then the uranium and thorium may have some correlation with F and Cl contents which can be mirrored by the peralkalinity. Plots of uranium against F and Cl contents are shown. The positive correlation indicates that the uranium enrichments are associated with the halogen contents. There seems to be a greater correlation for U against Cl than F indicating that the U may be transported preferentially as Cl complexes.

Black, S.↗