Prediction of dissociation pressures of mixed gas hydrates from data for hydrates of pure gases with water.
Dissociation pressures of mixed gas hydrates predicted from data for hydrates of methane, propane and nitrogen with water
PROPANE↗
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Hydrates at high pressures. i - methane-water, argon-water, and nitrogen-water systems.
Effect of high pressure on gas hydrate equilibrium curve determined experimentally for methane, argon and nitrogen hydrates
HYDRATE↗
The chemistry of comets
Comets appear to represent a population of rather homogeneous objects. In particular, the original size distribution peaks at a mean diameter of the order of 10 km. Cometary dust grains appear to be made of clusters of extremely fine particles (0.1-1.0 micron) sintered by heat at a variable degree during their perihelion passages. The brightness laws of comets appear to be derived only by the sublimation of water ice or at least of gas hydrates of the clathrate type. Pristine nuclei are likely to be radially undifferentiated; only their crustal surface must be outgassed and sintered by the heat of perihelion passages. Comet Halley is confirmed to be in the same general class as the bright comets of the 1970s. With an organic fraction of 33 percent in the cometary dust, the carbon of Comet Halley is close to cosmic abundances.
Delsemme, A. H.↗
The end-Permian mass extinction: A complex, multicausal extinction
The end-Permian mass extinction was the most extensive in the history of life and remains one of the most complex. Understanding its causes is particularly important because it anchors the putative 26-m.y. pattern of periodic extinction. However, there is no good evidence for an impact and this extinction appears to be more complex than others, involving at least three phases. The first began with the onset of a marine regression during the Late Permian and resulting elimination of most marine basins, reduction in habitat area, and increased climatic instability; the first pulse of tetrapod extinctions occurred in South Africa at this time. The second phase involved increased regression in many areas (although apparently not in South China) and heightened climatic instability and environmental degradation. Release of gas hydrates, oxidation of marine carbon, and the eruption of the Siberian flood basalts occurred during this phase. The final phase of the extinction episode began with the earliest Triassic marine regression and destruction of nearshore continental habitats. Some evidence suggests oceanic anoxia may have developed during the final phase of the extinction, although it appears to have been insufficient to the sole cause of the extinction.
Erwin, D. H.↗
The properties of clusters in the gas phase. IV - Complexes of H2O and HNOx clustering on NOx/-/
Thermodynamic quantities for the gas-phase clustering equilibria of NO2(-) and NO3(-) were determined with high-pressure mass spectrometry. A comparison of values of the free energy of hydration derived from the data shows good agreement with formerly reported values at 296 K. New data for larger NO2(-) and NO3(-) hydrates as well as NO2(-)(HNO2)n were obtained in this study. To aid in understanding the bonding and stability of the hydrates of nitrite and nitrate ions, CNDO/2 calculations were performed, and the results are discussed. A correlation between the aqueous-phase total hydration enthalpy of a single ion and its gas-phase hydration enthalpy was obtained. Atmospheric implications of the data are also briefly discussed.
Lee, N.↗
Hydrates at high pressures. iii - methane- argon-water, argon-nitrogen-water system.
Initial hydrate formation conditions for selected mixtures of argon-methane and argon-nitrogen determined through measurements of equilibrium pressures and temperature
CHEMICAL KINETICS↗
Clathrate hydrates in the solar system
Clathrate hydrates are crystalline compounds in which an expanded ice lattice forms cages that contain gas molecules. There are two principal hydrate structures. Structure I, with a 12 A cubic unit cell, contains 46 water molecules and 8 cages of two types, giving an ideal formula (for CH4) of CH4.5.75H2O. The actual formula contains somewhat more water as the cages are not completely filled. Other examples that form Structure I hydrates are C2H6, C2H4, C2H2, CO2, SO2, OCS, Xe, H2S. Structure II, with a 17 A cubic unit cell, contains 136 water molecules, and 8 large and 16 small cages. The ideal formula for CHCl3 is CHCL3.17H2O. Other examples of Structure II hydrates include C3H8, C2H5Cl, acetone, and tetrahydrofuran. Small molecules such as Ar, Kr and probably N2 and O2 also form a Structure II hydrate. The small molecules occupy both the large and small cages, giving an ideal formula of Ar.5.67H2O. The conditions of pressure and temperature for hydrate formation are discussed.
Miller, S. L.↗
Low-pressure clathrate-hydrate formation in amorphous astrophysical ice analogs
In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects.
Blake, D. F.↗
Trapping of gas mixtures by amorphous water ice
Our studies on gas trapping in amorphous water ice at 24-100 K were extended, by using mixtures of CH4, CO, N2, and Ar, rather than single gases. In 1:1 gas:(water vapor) mixtures, the competition among these gases on the available sites in the ice showed that the trapping capacity for the various gases is determined not only by the structure and dynamics of the ice, but is also influenced by the gas itself. Whereas at 24-35 K all four gases are trapped in the ice indiscriminantly, at 50-75 K there is a clear enhancement, in the order of CH4 > CO > N2 > or approximately Ar. This order is influenced by the gas-water interaction energy, the size of the trapped gas atom or molecule, the type of clathrate-hydrate formed (I or II) and, possibly, other factors. It seems that the gas can be trapped in the amorphous ice in several different locations, each being affected in a different way by the deposition temperature and gas composition. Once a gas atom or molecule is trapped in a specific location, it is predestined to emerge in one of eight different temperature ranges, which are associated with changes in the ice. The experimentally observed enhancements, together with the findings on the gas composition of comet Halley, might enable an estimation of the gas composition in the region of comet formation.
NASA Discipline Number 52-10↗
Non-solar noble gas abundances in the atmosphere of Jupiter
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, Jonathan I.↗
Getting water from the water of hydration on Mars
Both Viking landers found evidence of water in small concentration in the soils of Mars. Using the gas chromatograph mass spectrometer the soil samples on Mars were heated to 500 C to release the water. This result lead researchers to believe that the water in the soil of Mars was tightly bound in a hydration state. In the laboratory several Mars analog soils and a few bench mark soils were run through a microwave to determine the amount of water released using this method. The results suggest that sufficient water can be obtained using this method to augment the activities of a human base on Mars.
Gwynne, O.↗
Water in Lunar Materials
Two lines of evidence, suggest independently that materials which formed the Moon were not anhydrous: 1. Meteorites, our only sample of extraterrestrial material, contain water in varying amounts. Chondrites average about 0.25% water by weight. Carbonaceous chondrites, however, contain up to 20% water; and, although much of this water may be adsorbed atmospheric and surface water, the abundance of silicate hydrates in these objects indicates that considerable water existed in these meteorites before Earth impact. 2. The gas emission from Alphonsus observed by Kosyrev indicates that volatiles are diffusing out of the Moon. The observed emission was a C, band. Analyses of presumably juvenile gases reaching the Earth's surface show that water generally composes 95% or more of the gas. By analogy, it is suggested that water must be reaching the lunar surface. Consequently, it is reasonable to conclude that water existed in the materials which formed the Moon as well as those which formed the Earth or meteorites (or their source object). An estimate of the water content of the primordial Earth is 0.03%.
Speed, R. C.↗
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.↗
Project Explorer's unique experiments: Get Away Special #007
The Project Explorer payload represents the first attempt at broadcasting digitized voice signals via a Space Shuttle flight on amateur radio frequencies. These amateur ham-radio frequencies will be transmitting real time data while the experiments are operating. Experiments 1, 2, and 3 represent the work of students ranging from materials processing to the science of biology. Experiment 1 will study the solidification of two hypereutectic alloys, lead-antimony and aluminum-copper. Experiment 2 will investigate the examination and growth of radish seeds in space. Experiment 3 will examine the electrochemical growth process of potassium tetrocyonoplatinate hydrate crystals and Experiment 4 involves amateur radio transmissions, monitoring and support of the entire Get Away Special (GAS) 007 payload.
Arthur J. Henderson, Jr.↗
Far-infrared spectra of CO2 clathrate hydrate frosts
As a product of our interest in remote sensing of planetary ices, frost samples of CO2 clathrate hydrate were grown by depositing water vapor on a cooled surface and pressurizing the resulting water frost with CO2 gas. At pressures above the dissociation pressure of the clathrate, the samples exhibit an absorption peak at 75 cm (sup -1). At pressures below the dissociation pressure, the peak disappears. Since the free CO2 molecule does not have rotational or vibrational absorption in this region, the absorption is attributed to a CO2 rattling mode within a clathrate cage.
Landry, J. C.↗
Photochemistry of SO2 in Venus' upper cloud layers
The photochemical and transport processes that occur in the Venusian atmosphere in and above the upper cloud region are characterized with attention to the correlation with the Pioneer Venus spectrometer results for the cloud top SO2 distribution. The model uses upward-flowing SO2 and H2O to replace the sulfur and hydrogen lost through the lower boundary by the settling of sulfuric acid aerosols. Oxygen for the oxidation of SO2 to SO3 prior to hydration to H2SO4 is supplied by the photolysis of CO2. A model with SO2 as the major sulfur-bearing gas is consistent with the Pioneer data.
Winick, J. R.↗
Properties of clusters in the gas phase. V - Complexes of neutral molecules onto negative ions
Ion-molecules association reactions of the form A(-)(B)n-1 + B = A(-)(B)n were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl(-), I(-), and NO2(-) with n ranging from one to three or four, and onto SO2(-) and SO3(-) with n equal to one; and (2) carbon dioxide onto Cl(-), I(-), NO2(-), CO3(-), and SO3(-) with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions.
Keesee, R. G.↗
Stratospheric aircraft exhaust plume and wake chemistry studies
This report documents progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere. Estimates are given for the emissions, summarizing relevant earlier work (CIAP) and reviewing current propulsion research efforts. The chemical evolution and the mixing and vortical motion of the exhaust are analyzed to track the exhaust and its speciation as the emissions are mixed to atmospheric scales. The species tracked include those that could be heterogeneously reactive on the surfaces of the condensed solid water (ice) particles and on exhaust soot particle surfaces. Dispersion and reaction of chemical constituents in the far wake are studied with a Lagrangian air parcel model, in conjunction with a radiation code to calculate the net heating/cooling. Laboratory measurements of heterogeneous chemistry of aqueous sulfuric acid and nitric acid hydrates are also described. Results include the solubility of HCl in sulfuric acid which is a key parameter for modeling stratospheric processing. We also report initial results for condensation of nitric acid trihydrate from gas phase H2O and HNO3.
Miake-Lye, R. C.↗