Xenon Hexafluoride: Structure of a Cubic Phase at -80{degrees}C

The crystal structure of a cubic phase of composition XeF(6) has been determined at -80 degrees C. There are no simple molecules in the complex structure which involves 1008 atoms distributed over 1600 positions per unit cell. Ions of XeF(5)+ and F- are associated in tetrameric and hexameric rings of point group symmetries 4 and 32, respectively. The structure contains right-and left-handed conformations of both tetramers and hexamers. The handedness of the tetramers is dis-ordered but the orientation is ordered. The handedness of the hexamers is ordered but the orientation is disordered.     

Crystal Structure of Benzene II at 25 Kilobars

Crystals of a high-pressure form of benzene (benzene 11) were grown in the diamond-anvil pressure cell at elevated temperature and pressure from the transition of solid I to solid II. X-ray precession data were obtained from a single-crystal in the high-pressure cell. At 21 degrees C and about 25 kilobars, benzene II crystallizes in the monoclinic system with a = 5.417 +/- 0.005 angstroms (S.D.), b = 5.376 +/- 0.019 angstroms, c = 7.532 +/- 0.007 angstroms, beta = 110.00 degrees +/- 0.08 degrees , space group P2(1)/ c, Pc= 1.26 grams per cubic centimeter. The crystal structure was solved by generating all possible molecular packing configurations and calculating structure factors, reliability factors, and packing energies for each configuration. This procedure produced a unique solution for the molecular packing of benzene II.     

Antiprismatic Coordination about Xenon: The Structure of Nitrosonium Octafluoroxenate(VI)

The structure of nitrosonium octafluoroxenate(VI), 2NOF . XeF(6), has been determined by means of single-crystal x-ray counter methods (R-index = 0.046, weighted R-index = 0.042). The space group is Pnma, with a = 8.914(10) angstroms, b = 5.945(10) angstroms, and c = 12.83(2) angstroms (the numbers in parentheses are the standard deviations to the least significant digit or digits); the calculated density (rho) is 3.354 grams per cubic centimeter, and there are four formula units per unit cell. The material consists of well-separated NO(+) and (XeF(8))(2-) ions; the structural formula is thus (NO)(2) (XeF(8)). The anion configuration is that of a slightly distorted Archimedean antiprism. The observed distortion appears incompatible with a lone-pair repulsion model. Xenon-fluorine bond lengths of 1.971(7), 1.946(5), 1.958(7), 2.052(5), and 2.099(5) angstroms were found.     

Phase Transformation at High Temperatures in Hafnia and Zirconia

Phase transformation curves for HfO(2) and ZrO(2) have been made. Transformation hysteresis is discussed. The transformation of monoclinic to tetragonal as temperature increases occurs over the range 1000 degrees to 1200 degrees C in ZrO(2), and 1500 degrees to 1600 degrees C in HfO(2). With decreasing temperature the transition back to monoclinic occurs from 970 degrees to 750 degrees C in ZrO(2) and 1550 degrees to 1450 degrees C in HfO(2). These transformations have been visually observed in ZrO(2), but not in HfO(2).     

Xenon Oxyfluoride

The incomplete hydrolysis of XeF(6) has been used to prepare a xenon oxyfluoride, XeOF(4). The latter is a clear, colorless liquid, freezing at -41 degrees C. The infrared and Raman spectra show that the XeOF(4) molecule has a fourfold symmetry axis. The large Xe-O stretching force constant indicates the Xe-O bond has appreciable double bond character.     

Monoclinic hydroxyapatite

The existence of a monoclinic phase of hydroxyapatite, Ca(2)(PO(4))(4)OH, has been confirmed, by single-crystal structure analysis (weighted "reliability" factor = 3.9 percent on |F|(2)). The structure has space group P21/b, a = 9.4214(8) angstroms, b = 2a, c = 6.8814(7) angstroms, and gamma = 120 degrees , and is analogous to that of chlorapatite. The distortions from the hexagonal structure with which the monoclinic structure is pseudosymmetric are similar to those in chlorapatite, including enlargement of that triangular array of oxygen atoms in which the chlorine ion or, in hydroxyapatite, the hydroxyl hydrogen ion is approximately centered. The hydroxyapatite specimen was prepared by the conversion of a single crystal of chlorapatite in steam at 1200 degrees C, was mimetically twinned, and was approximately 37 percent monoclinic.     

Shock-wave compression and x-ray studies of titanium dioxide

The Hugoniot of the rutile phase of titanium dioxide has been determined to 1.25 megabars, and data show the existence of a phase change at about 0.33 megabar. The volume decrease associated with this transformation appears to be quite large (approximately 21 percent). Rutile, when recovered from shockloading in excess of the transformation pressure, is found to be irreversibly transformed to the orthorhombic lead dioxide structure (a distortion of the fluorite structure) with parameters a, 4.529; b, 5.464; and c, 4.905 angstroms and a calculated density of 4.374 grams per cubic centimeter. The new phase reverts to rutile at temperatures above 450 degrees C. It is suggested that the new phase may be another diagnostic indicator of meteorite impact on the earth's surface.     

Crystal Structure of the Solid Electrolyte(C5H5NH) Ag5I6 at -30{degrees}C

The crystal structure of pyridinium hexaiodopentaargentate, (C(5)H(5)NH) Ag(5)l(6), is unique among those of the halide and chalcogenide solid electrolytes in that face-sharing iodide octahedra as well as face-sharing tetrahedra and face-sharing between octahedra and tetrahedra provide the paths for silver ion transport. There are two formula units in a hexagonal cell, space group P6/mcc (D6h(2)). At -30 degrees C, the lattice constants are a = 11.97 +/- 0.02, c = 7.41 +/- 0.01 A. The structure has three sets of sites for the silver ions. At -30 degrees C two of these sets are apparently filled with the ten silver ions per unit cell, while the third set of tetrahedrally coordinated general positions is empty. Therefore, the conductivity at this temperature is limited by the thermal excitation of the silver ions into the empty tetrahedra.     

A Redox Fuel Cell That Operates with Methane as Fuel at 120{degrees}C

Platinum black efficiently catalyzes the oxidation of methane by iron(III) to generate carbon dioxide and eight equivalents of iron(II) in solutions of sulfuric acid in water. The rate of oxidation increases over 4 hours to reach approximately 4.83 x 10(-2) moles of iron(II) per gram atom of surface platinum per second. A redox fuel cell was assembled that used this reaction in a liquid reformer to generate soluble reducing equivalents of iron(II) from methane, which was electrochemically oxidized to iron(III) in the cell. A vanadium(V)-(IV)-nitric acid-O(2) redox system catalyzed the electrochemical reduction of O(2). The open-circuit voltage of the cell was 0.48 volt, and the maximum power output of the cell was 8.1 milliwatts per cubic centimeter of graphite felt electrode.     

The silica-alumina system: stable and metastable equilibria at 1.0 atmosphere

Diffusion couples, consisting of sapphire and fused silica, which were annealed in the temperature range from 1678 degrees to 2003 degrees C and analyzed by electron beam microprobe, have provided data on the stable phase equilibrium of the silica-alumina system. Under stable equilibrium conditions, the intermediate compound of this system, mullite (3Al(2)O(3) . 2SiO(2)), melts incongruently at 1828 degrees +/- 10 degrees C and its solid solution field extends from 70.5 to 74.0 percent (by weight) alumina. The stable phase diagram is a composite of the two binary eutectic diagrams: silica-mullite in the absence of alumina and silica-alumina in the absence of mullite. Under metastable conditions, mullite melts congruently at approximately 1890 degrees +/- 10 degrees C and its solid solution field extends to approximately 83.2 percent (by weight) alumina.     

Ammonioborite: new borate polyion and its structure

The mineral ammonioborite is monoclinic with unit cell dimensions (in angstroms): a = 25.27, b = 9.65, and c = 11.56; beta = 94 degrees 17', and the space group is C 2/c. Analysis of the crystal structure revealed the crystallo-chemical formula (NH(4))(3)B(15)O(20)(OH)(8).4H(2)O, with four such formula units in the unit cell. The basic structural unit is the double ring consisting of one BO(4) tetrahedron and four BO(3) triangles: in ammonioborite three of these units are connected to give trimeric ions [B(15)O(20)(OH)(8)](3-).     

Kinetics of the fe2+-mg, order-disorder reaction in anthophyllites: quantitative cooling rates

The kinetics of the Fe(2+)-Mg, order-disorder phenomenon in a highly ordered natural anthophyllite have been determined over the temperature range from 400 degrees to 720 degrees C at a pressure of 2 kilobars. At temperatures of 600 degrees C and above, equilibrium is attained by disordering as well as ordering reactions. The intracrystalline exchange is defined by a standard Gibbs free energy of 4247 +/- 54 calories per formula unit. Rate studies at 550 degrees and 500 degrees C show that equilibrium is attained by ordering but not by disordering within the same time scale and that the exchange reaction is characterized by an activation energy of approximately 55 kilocalories per formula unit. An equilibration temperature for the natural anthophyllite of 270 degrees C is determined from the termination of the ordering process owing to excessively slow reaction kinetics after approximately 10(7) years. From the rate constants of the exchange process, for different crystallization temperatures, the apparent equilibration temperature of 270 degrees C defines a maximum linear cooling rate for the rock of 1 x 10(4) degrees C per year.     

Survival of mouse embryos frozen to -196 degrees and -269 degrees C

Mouse embryos survived freezing to -196 degrees C. Survival required slow cooling (0.3 degrees to 2 degrees C per minute) and slow warming (4 degrees to 25 degrees C per minute). Depending on the specific rates used, 50 to 70 percent of more than 2500 frozen and thawed early embryos developed into blastocysts in culture after storage at -196 degrees C for up to 8 days. When approximately 1000 of the survivors, including some frozen to -269 degrees C (4 degrees K), were transferred into foster mothers, 65 percent of the recipients became pregnant. More than 40 percent of the embryos in these pregnant mice gave rise to normal, living full-term fetuses or newborn mice.     

The charnockite geotherm

Charnockite, a hypersthene-bearing granite, and other associated rocks of the charnockite series have a global distribution. These rocks, according to evidence from mineral-chemical and experimental phase equilibrium relations, formed or recrystallized at temperatures between 800 degrees and 900 degrees C and at relatively shallow depths of 6 to 12 kilometers. This evidence indicates the existence of geothermal gradients of 70 degrees to 100 degrees C per kilometer probably at various times, the latest being around 1300 x 10(6) years ago.     

Comet giacobini-zinner: in situ observations of energetic heavy ions

Conclusive evidence is presented for the existence of energetic ( approximately 535,0000 to 150,000 electron volts), heavy (>-12 atomic mass units), singly charged cometary ions within approximately 1.5 x 10(6) kilometers of comet Giacobini-Zinner. The observations were made with the University of Maryland/Max-Planck-Institut ultralow-energy charge analyzer on, the International Cometary Explorer spacecraft. The most direct evidence for establishing the mass of these ions was obtained from an analysis of the energy signals in one of the solid-state detectors; it is significant at the three-sigma level. Maximum fluxes were recorded approximately 1 hour before and approximately 1 hour after closest approach to the cometary nucleus. Transformation of the particle angular distributions observed at approximately 50,000 kilometers radial distance from the comet during the inbound pass into a rest frame in which the distributions are nearly isotropic requires a transformation velocity that is consistent with the local solar wind velocity if one assumes that these particles are primarily singly ionized with a mass of 18 +/- 6 atomic mass units. The existence of a frame of reference in which these water-group ions were isotropic implies that they underwent strong pitch angle scattering after their ionization. Particle energies in the rest frame extend to substantially higher values than would be expected if these ions were locally ionized and then picked up by the solar wind, implying that the ions were accelerated or heated. The derived ion density, approximately 0.1 per cubic centimeter, is consistent with a crude model for the production and transport of pickup ions.     

An ultradense polymorph of rutile with seven-coordinated titanium from the Ries crater

We report the discovery of an ultradense post-rutile polymorph of titanium dioxide in shocked gneisses of the Ries crater in Germany. The microscopic diagnostic feature is intense blue internal reflections in crossed polarizers in reflected light. X-ray diffraction studies revealed a monoclinic lattice, isostructural with the baddeleyite ZrO2 polymorph, and the titanium cation is coordinated with seven oxygen anions. The cell parameters are as follows: a = 4.606(2) angstroms, b = 4.986(3) angstroms, c = 4.933(3) angstroms, beta (angle between c and a axes) = 99.17(6) degrees; space group P2(1)/c; density = 4.72 grams per cubic centimeter, where the numbers in parentheses are standard deviations in the last significant digits. This phase is 11% denser than rutile. The mineral is sensitive to x-ray irradiation and tends to invert to rutile. The presence of baddeleyite-type TiO2 in the shocked rocks indicates that the peak shock pressure was between 16 and 20 gigapascals, and the post-shock temperature was much lower than 500 degrees C.     

Open Framework Structures Based on Sex2- Fragments: Synthesis of (Ph4P)[M(Se6)2] (M = Ga, In, TI) in Molten (Ph4P)2Sex

Polychalcogenide compounds with open polymeric frameworks are rare, and they represent a class of compounds in which microporosity might be achieved. Microporous frameworks that are not oxide-based are now attracting interest because of the combination of catalytic and electronic properties they may simultaneously possess. Three new compounds that may be forerunners to such materials have been discovered and are reported here. The reaction of gallium (Ga), indium (In), and thallium (TI) metal with (Ph(4)P)(2)Se(5) (Ph, phenyl) and an excess of elemental selenium (Se) in a sealed, evacuated Pyrex tube at 200 degrees C yielded small red crystals of (Ph(4)P)[Ga(Se(6))(2)] (I), (Ph(4)P)[In(Se(6))(2)] (II), and (Ph(4)P)[TI(Se(6))(2)] (III), respectively. The [M(Se(6))(2)](-) (M = Ga, In, TI) ions form a two-dimensional, open framework filled with Ph(4)P(+) ions. The [M(Se(6))(2)](n)(n-) structure consists of tetrahedral M(3+) centers and bridging Se(6)(2-) ligands, leading to an extended structure in two dimensions. These layers stack perfectly one on top of the other giving rise to one-dimensional channels running down the c axis that are filled with Ph(4)P(+) cations. These cations are situated in the layers, as opposed to between the layers, and the whole structure can be viewed as a template. Compound II shows remarkable thermal stability and melts congruently at 242 degrees C. Upon cooling to room temperature it gives a glassy phase that recrystallizes upon subsequent heating to 160 degrees C.     

Geometry of the Perxenate Ion

A three-dimensional x-ray analylsis of a crystallinie solid of Xe(+8) formed by the reaction of XeF(6) with sodium hydroxide solution indicates that it is sodium perxenate octahydrate, Na(4)XeO(6) * 8H(2)O. The perxenate ion, XeO(6)(-4), has approximately a regular octahedral configuration with a mean xenon-oxygen bond length of 1.875 A.     

Water and carbon in rusty lunar rock 66095

Lunar rock 66095 contains a hydrated iron oxide and has an unusual amount of water for a lunar rock (140 to 750 parts per million), 90 percent of which is released below 690 degrees C. The deltaof water released at these low temperatures varies from -75 to -140 per mil relative to standard mean ocean water (SMOW). The small amount of water released between 690 degrees and 1300 degrees C has a delta of about -175 +/-25 per mil SMOW. These delta values are not unusual for terrestrial water. The delta(18)O of water extracted from 110 degrees to 400 degrees C has a value of +5+/- I per mil SMOW, similar to the value for lunar silicates from rock 66095 and different from the value of -4 to -22 per mil found for samples of terrestrial rust including samples of rusted meteoritic iron. The amount of carbon varies from 11 to 59 parts per million with a delta(13)C from -20 to -30 per mil relative to Pee Dee belemnite. Only very small amounts of reduced species (such as hydrogen, carbon monoxide, and methane) were found, in contrast to the analyses of other lunar rocks. Although it is possible that most of the water in the iron oxide (goethite) may be terrestrial in origin or may have exchanged with terrestrial water during sample return and handling, evidence presented herein suggests that this did not happen and that some lunar water may have a deltaD that is indistinguishable from that of terrestrial water.     

Composition of Aqueous Solutions in Equilibrium with Sulfides and Oxides of Iron at 350{degrees}C

Solutions of potassium chloride (pH-buffered and 1-molal) equilibrated at 350 degrees C with pyrrhotite, pyrite, and magnetite contained approximately 1 millimole of reduced sulfur and less than 0.1 millimole of oxidized sulfur per kilogram. Similar solutions equilibrated with pyrite, magnetite, and hematite contained approximately 1 millimole of reduced sulfur, but 3 to 6 millimoles of oxidized sulfur per kilogram. Both types of solutions contained less than 0.1 millimole of iron per kilogram at pH >/= 6 and approximately 100 millimoles per kilogram at pH 2.