Hydrate formation in the system n-propanol–water

The phase diagram of the binary system n-propanol alcohol–water was investigated with use of differential thermal analysis and powder X-ray diffraction. The phase diagram has three groups of thermal effects, which can be considered as peritectic melting of three different hydrates (?60.0, ?53.5, and ?41.5 °C). At the same time, powder X-ray diffraction data indicate the existence of only one compound in this system (cubic unit cell, a = 12.09 ± 0.01 Å and 12.15 ± 0.01 Å at ?109 to ?66 °C, respectively). The most probable explanation of this contradiction seems to be the existence of several hydrates belonging to the same structural type but different in composition.     

Powder diffraction and Raman spectroscopic study of lawsonite at high water pressure

The structural behavior of natural lawsonite CaAl₂Si₂O₇(OH)₂ · H₂O in aqueous and nonaqueous media (pressure up to 9.5 GPa) has been studied by synchrotron powder diffraction and Raman spectroscopy. The volume compressibility of lawsonite is found to be similar in both aqueous and nonaqueous media, while irreversible amorphization is observed only under compression in the aqueous medium to a pressure of about 6 GPa. Along with the observed increase in framework vibration frequencies, this reveals that the lawsonite structure is unstable when hydrostatic conditions of compression differ from those provided by crystallization of ice VII in an aqueous medium.     

Structure of the intermediate high-pressure phases of ternary lead tellurides

In chambers with diamond anvils, the structure of high-pressure phases of ternary lead tellurides Pb_1?x Sn_xTe (x = 0.29) and Pb_1?x Mn_xTe (x = 0.05) and nonstoichiometric crystals Pb_0.55Te_0.45, Pb_0.45Te_0.55 is analyzed by the synchrotron radiation diffraction method at pressures of P up to 14 GPa. The orthorhombic structure of the intermediate high-pressure phase (space group Pnma) is determined for all the samples above 6 GPa. Models of the phase transition in PbTe from the initial rock salt structure to the orthorhombic phase, which constitutes a distorted variant of NaCl, as well as the properties of this phase, are discussed.     

High-pressure clathrate hydrate of acetone

X-ray diffraction study of quenched sample of acetone clathrate hydrate synthesized at 0.8 GPa was carried out. It was shown that the host frameworks of the hydrate comprise uniform cavities which are similar to that of recently characterized structure of high-pressure tetrahydrofurane hydrate. The unique peculiarity of investigated hydrate is decrease in the crystallographic symmetry of the hydrate arising from ordering in guest subsystem.     

Gas hydrates of argon and methane synthesized at high pressures: composition, thermal expansion, and self-preservation

For the first time, the compositions of argon and methane high-pressure gas hydrates have been directly determined. The studied samples of the gas hydrates were prepared under high-pressure conditions and quenched at 77 K. The composition of the argon hydrate (structure H, stable at 460-770 MPa) was found to be Ar.(3.27 +/- 0.17)H(2)O. This result shows a good agreement with the refinement of the argon hydrate structure using neutron powder diffraction data and helps to rationalize the evolution of hydrate structures in the Ar-H(2)O system at high pressures. The quenched argon hydrate was found to dissociate in two steps. The first step (170-190 K) corresponds to a partial dissociation of the hydrate and the self-preservation of a residual part of the hydrate with an ice cover. Presumably, significant amounts of ice Ic form at this stage. The second step (210-230 K) corresponds to the dissociation of the residual part of the hydrate. The composition of the methane hydrate (cubic structure I, stable up to 620 MPa) was found to be CH(4).5.76H(2)O. Temperature dependence of the unit cell parameters for both hydrates has been also studied. Calculated from these results, the thermal expansivities for the structure H argon hydrate are alpha(a) = 76.6 K(-1) and alpha(c) = 77.4 K(-1) (in the 100-250 K temperature range) and for the cubic structure I methane hydrate are alpha(a) = 32.2 K(-1), alpha(a) = 53.0 K(-1), and alpha(a) = 73.5 K(-1) at 100, 150, and 200 K, respectively.     

The application of <Emphasis Type="Italic">in situ</Emphasis> X-ray diffraction for the study of mineral reactions: The formation of lawsonite at 400°C and 25 kbar

The method of in situ X-ray diffraction with the influence of temperature and pressure on the sample was successfully applied in Siberian Synchrotron and Terahertz Radiation Centre on the experimental station Diffractometry in hard X-rays. High-pressure water-containing lawsonite silicate CaAl₂[Si₂O₇](OH)₂·H₂O is obtained at 400°C and 25 kbar in a diamond anvil cell during the decomposition of laumontite. In situ diffractometry of the reaction products helps to determine parameters of the unit cell of lawsonite and phase composition of CaO-Al₂O₃-SiO₂-H₂O at 400°C and 25 kbar.     

Clathrate Hydrates of Sulfur Hexafluoride at High Pressures

The pressure dependence (0.4 Mpa–1.3 GPa) of the hydrate decomposition temperatures in the sulfur hexafluoride-water system has been studied. In addition to the known low-pressure hydrate SF₆17H₂O of Cubic Structure II, two new high-pressure hydrates have been found. X-ray analysis in situ showed the gas hydrate forming in the sulfur hexafluoride-water system above 50 MPa at room temperature to be of Cubic Structure I. The ability of water to form hydrates whose structures depend on the guest molecule size under normal conditions and at high pressures is discussed.     

Structural transformations in mechanochemical synthesis of solid solutions in the Cu-Ga system

Formation of solid solutions in the copper-gallium system under mechanical activation is considered as an example of a mechanochemical interaction between a solid metal and a liquid metal.     

Phase diagram and high-pressure boundary of hydrate formation in the ethane-water system

Dissociation temperatures of gas hydrate formed in the ethane-water system were studied at pressures up to 1500 MPa. In situ neutron diffraction analysis and X-ray diffraction analysis in a diamond anvil cell showed that the gas hydrate formed in the ethane-water system at 340, 700, and 1840 MPa and room temperature belongs to the cubic structure I (CS-I). Raman spectra of C-C vibrations of ethane molecules in the hydrate phase, as well as the spectra of solid and liquid ethane under high-pressure conditions were studied at pressures up to 6900 MPa. Within 170-3600 MPa Raman shift of the C-C vibration mode of ethane in the hydrate phase did not show any discontinuities, which could be evidence of possible phase transformations. The upper pressure boundary of high-pressure hydrate existence was discovered at the pressure of 3600 MPa. This boundary corresponds to decomposition of the hydrate to solid ethane and ice VII. The type of phase diagram of ethane-water system was proposed in the pressure range of hydrate formation (0-3600 MPa).