Search NASA⌕ Search

SEARCH · Search NASA

Results for “Clathrate”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

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.↗
NASA NTRS1991

Clathrate type 2 hydrate formation in vacuo under astrophysical conditions

The properties of clathrate hydrates were used to explain the complex and poorly understood physical processes taking place within cometary nuclei and other icy solar system bodies. Most of all the experiments previously conducted used starting compositions which would yield clathrate types I hydrates. The main criterion for type I vs. type II clathrate hydrate formation is the size of the guest molecule. The stoichiometry of the two structure types is also quite different. In addition, the larger molecules which would form type II clathrate hydrates typically have lower vapor pressures. The result of these considerations is that at temperatures where we identified clathrate formation (120-130 K), it is more likely that type II clathrate hydrates will form. We also formed clathrate II hydrates of methanol by direct vapor deposition in the temperature range 125-135 K.

Blake, D. F.↗
NASA NTRS1988

Clathrate hydrates in cometary nuclei and porosity

Possible mechanisms of formation and decomposition of CO2-clathrate hydrate in cometary nuclei are discussed. As far as it is known, this is the only clathrate hydrate which is unstable at low temperatures. Calculation shows that, in accord with other evidence, neither volume nor grain boundary diffusion in the clathrate lattice can be responsible for the rate of these reactions and that a surface mechanism with the attendant sensitivity to pressure must play a crucial role. Density changes accompanying CO2-clathrate decomposition and formation can lead to microporosity and enhanced brittleness or even to fracture of cometary nuclei at low temperatures. Other clathrate hydrates and mixed clathrates are also discussed.

Smoluchowski, R.↗
NASA NTRS1991

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.↗
NASA NTRS1980

A model for the formation and stabilization of charged water clathrates

A model for the formation and stabilization of charged water clathrates is presented which accounts for observed anomalies in H(+)(H2O)n ion distributions. These anomalies are observed in both ion cluster and neutral expansions and are consistent with the sizes expected for clathrate ions. That the same sizes are observed in both ion cluster and neutral expansions strongly suggests that a rapid ionic process is responsible for their formation. The proposed model is based on the high mobility and bonding effects of the excess proton in water. Computer simulations suggest that excess proton movement in a water clathrate would be suitable for stabilizing the clathrate structure as well as giving it access to a large number of nearly degenerate proton configurations. The formation of clathrates in charged water clusters of proper size can be ascribed to the following: rapid excess proton movement, a strong preference of the H3O(+) for a three-coordinate bonding structure (which is compatible with hydrogen bonding), and finally, relatively slow processes leading to thermal disorder.

Holland, P. M.↗
NASA NTRS1993

Far-infrared investigations of a methanol clathrate hydrate - Implications for astronomical observations

Observations of nonterrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over 40 years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. We have prepared a methanol (CH3OH) clathrate hydrate, using a recently published procedure, and have investigated its far-infrared spectrum. The spectrum is quite different from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

Hudson, Reggie L.↗
NASA NTRS2004

Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates

Underground sequestration has been proposed as a novel method of permanent disposal of harmful gases emitted into the atmosphere as a result of human activity. The method was conceived primarily for disposal of carbon dioxide (CO2, greenhouse gas causing global warming), but could also be applied to CO, H2S, NOx, and chorofluorocarbons (CFCs, which are super greenhouse gases). The method is based on the fact that clathrate hydrates (e.g., CO2 6H2O) form naturally from the substances in question (e.g., CO2) and liquid water in the pores of sub-permafrost rocks at stabilizing pressures and temperatures. The proposed method would be volumetrically efficient: In the case of CO2, each volume of hydrate can contain as much as 184 volumes of gas. Temperature and pressure conditions that favor the formation of stable clathrate hydrates exist in depleted oil reservoirs that lie under permafrost. For example, CO2-6H2O forms naturally at a temperature of 0 C and pressure of 1.22 MPa. Using this measurement, it has been calculated that the minimum thickness of continuous permafrost needed to stabilize CO2 clathrate hydrate is only about 100 m, and the base of the permafrost is known to be considerably deeper at certain locations (e.g., about 600 m at Prudhoe Bay in Alaska). In this disposal method, the permafrost layers over the reservoirs would act as impermeable lids that would prevent dissociation of the clathrates and diffusion of the evolved gases up through pores.

Duxbury, N.↗
NASA NTRS1975

Carbon dioxide-water clathrate as a reservoir of CO2 on Mars

It has been suggested that the residual polar caps of Mars contain a resorvoir of permanently frozen carbon dioxide which is controlling the atmospheric pressure. However, observational data and models of the polar heat balance suggest that the temperatures of the Martian poles are too high for solid CO2 to survive permanently. On the other hand, the icelike compound carbon dioxide-water clathrate could function as a CO2 reservoir instead of solid CO2, because it is stable at higher temperatures. This paper shows that the permanent polar caps may contain several millibars of CO2 in the form of clathrate, and discusses the implications of this permanent clathrate reservoir for the present and past atmospheric pressure on Mars.

Dobrovolskis, A.↗
NASA NTRS1978

Ice clathrate as a possible source of the atmospheres of the terrestrial planets

The presence and compositions of atmospheres on the terrestrial planets do not follow directly from condensation models which would have earth accreting near 500 K. No single mechanism yet proposed adequately accounts for the abundances of noble gases and carbon and nitrogen in the atmospheres. We show that the composition of clathrates forming at low temperatures in cold regions of the nebula can be predicted. Addition of about 1 ppm clathrate material to the earth can explain observed abundances of Ar, Kr, and Xe. Condensation and adsorption processes occurring at 400-500 K are necessary to explain the observed abundances of Ne, H2O, C, and N. Possible sources of clathrates could be cometary bodies formed in the outer solar system.

Sill, G. T.↗
NASA NTRS1993

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.↗
NASA NTRS2006

The Location of the CO2, Fundamental in Clathrate Hydrates and its Application to Infrared Spectra of Icy Solar System Objects

CO2 is present on the surface of many Solar System objects, but not always as a segregated, pure ice. In pure CO2-ice, the fundamental absorption is located near 4.268 micron (2343.3 wavenumbers). However, on several objects, the CO2 fundamental is shifted to higher frequency. This shift may be produced by CO2 gas trapped in another material, or adsorbed onto minerals. We have seen that a mixture of H2O, CH3OH4 and CO2 forms a type II clathrate when heated to 125 K and produces a CO2 fundamental near 4.26 micron. The exact location of the feature is strongly dependent on the initial ratio of the three components. We are currently exploring various starting ratios relevant to the Solar System to determine the minimum amount of CH3OH needed to convert all of the CO2 to the clathrate, i.e. eliminate the splitting of the CO2 fundamental. We are testing the stability of the clathrate to thermal processing and UV photolysis, and documenting the changes seen in the spectra in the wavelength range from 1-5 micron. We acknowledge financial support from the Origins of Solar Systems Program, the Planetary Geology and Geophysics and the NASA Postdoctoral Program.

Sandford, S. A.↗
NASA NTRS2011

Analysis of Subsurface Clathrates in the Upper Crust of Titan

Titan has an atmosphere rich in methane, which should have long since been depleted unless a mechanism exists for storing this molecule below the surface. One hypothesis is that methane could be stored in the form of a clathrate hydrate, which is a structure with an ice lattice forming molecular cages in which gases are trapped. It is stable at low temperatures and over a wide range of pressures, suggesting that a clathrate hydrate may have stored methane on Titan from the beginning of its history.

methane↗
NASA NTRS2012

Measurement of Clathrate Hydrate Thermodynamic Stability in the Presence of Ammonia

There is a lack of data available for the stability of clathrate hydrates in the presence of ammonia for low-to-moderate pressures in the 0-10 MPa range. Providing such data will allow for a better understanding of natural mass transfer processes on celestial bodies like Titan and Enceladus, on which destabilization of clathrates may be responsible for replenishment of gases in the atmosphere. The experimental process utilizes a custom-built gas handling system (GHS) and a cryogenic calorimeter to allow for the efficient testing of samples under varying pressures and gas species.

clathrate hyudrates↗
NASA NTRS1983

The atmosphere of a dirty-clathrate cometary nucleus - A two-phase, multifluid model

The dynamical and thermal structure of a dirty-clathrate cometary nucleus' gas atmosphere is presently given a self-consistent, transonic multifluid solution in which, although the heavy neutron and ion species are treated as a single fluid in the collision-dominated region, the photoproduced H is treated separately. The thermal profile of the atmosphere thus obtained is entirely different from those predicted by the earlier, single-fluid models as well as the multifluid models which assumed equipartition of energy between electrons and ions. While the electron gas, like the neutrals and the ions, cools due to expansion, its main mode of energy loss in the inner coma is by way of inelastic collisions with the predominant H2O molecule. The high electron temperature in the outer coma also decreases the efficiency of electron removal by dissociative recombination, thereby increasing electron density throughout the coma.

Marconi, M. L.↗
NASA NTRS1985

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.↗