Eduard G. Larionov

Clathrate formation in water-noble gas (Hydrogen) systems at high pressures

Phase equilibria in helium-water, neon-water, and hxdrogen-water svstems were studied at pressures up to 15 kbar. The results are compared with the data for the previously investigated water systems with argon, crypton, and xenon. It is concluded that classical polyhedral clathrate hydrates are formed in all the systems, the stability of the hydrates diminishing from xenon to neon. In all the systems, except the xenon system, the hydrates are based on the crystalline framework of ice II. Their formation demands high pressures; the larger the guest molecule, the higher the pressure required. The xenon molecule seems to be too large to fit the cage of the ice II framework; therefore, the xenon hydrate CS-I remains stable up to at least 15 kbar.

Phase Diagram and High-Pressure Boundary of Hydrate Formation in the Carbon Dioxide−Water System

Experimental investigation of the phase diagram of the system carbon dioxide-water at pressures up to 2.7 GPa has been carried out in order to explain earlier controversial results on the decomposition curves of the hydrates formed in this system. According to X-ray diffraction data, solid and/or liquid phases of water and CO2 coexist in the system at room temperature within the pressure range from 0.8 to 2.6 GPa; no clathrate hydrates are observed. The results of neutron diffraction experiments involving the samples with different CO2/H2O molar ratios, and the data on the phase diagram of the system carbon dioxide-water show that CO2 hydrate of cubic structure I is the only clathrate phase present in this system under studied P-T conditions. We suppose that in the cubic structure I hydrate of CO2 multiple occupation of the large hydrate cavities with CO2 molecules takes place. At pressure of about 0.8 GPa this hydrate decomposes into components indicating the presence of the upper pressure boundary of the existence of clathrate hydrates in the system.

PHASE DIAGRAM OF THE XE-H2O SYSTEM UP TO 15 KBAR

The phase equilibria in the Xe–H2O system have been studied by the DTA technique under hydrostatic pressures up to 15 000 bar in a temperature range from -25 °C to 100 °C. We have shown that the cubic structure I xenon hydrate forming at ambient pressure does not undergo any phase transitions under the conditions studied. The temperature of its decomposition into water solution and gas (fluid) increases from 27 °C at 25 bar to 78.2 °C at 6150 bar. At higher pressures the hydrate decomposes into water solution and solid xenon. In the temperature range from 6800 to 9500 bar the decomposition temperature (79.0–79.5 °C) is practically independent of pressure, while further pressure increase results in a slow decrease to 67 °C at 15 000 bar.

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 SF6⋯17H2O 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.

CS-II binary clathrate hydrates at pressures of up to 15 kbar

The pressure dependence of the decomposition temperatures of binary clathrate hydrates of tetra-hydrofuran with xenon and methane as well as of chloroform and carbon tetrachloride clathrates with xenon has been studied. The absence of phase transitions at pressures from 1 to 15,000 bar indicates that the structure of all the hydrates remains constant (CS-II). The decomposition temperatures of the binary hydrates of tetrahydrofuran and carbon tetrachloride with xenon at 15 kbar (above 124ℴC) are exceedingly high for polyhedral clathrate hydrates because the guest molecules are highly complementary to the cavities of the clathrate lattice. The paper also considers the packing density effect in the crystal structure of hydrates on the behavior of the latter at elevated pressure.

Gas‐Hydrate Packing and Stability at High Pressures

The decomposition temperatures of double gas hydrates of tetrahydrofuran with noble gases from krypton to helium at pressures up to 15 kbar were found by differential thermal analysis. The stability of hydrates was shown to rise as their packing coefficient increases. Krypton and argon hydrates retain the original cubic structure II in the whole pressure range. In neon and helium systems, polyhedral double hydrates have upper stability limits at 7.4 and 6.0 kbar, respectively.

Phase Diagrams of the Ternary Gas Hydrate Forming Systems at High Pressures. Part 1. Propane–Methane–Water System

Abstract Cross sections of the ternary system propane–methane–water at pressure up to 15 kbar have been investigated by means of differential thermal analysis. It is stated that a double gas hydrate of the cubic structure II is formed in the system. It is stable within the whole pressure range investigated. It is most likely that at pressures above 3.4 kbar one more double hydrate exists in the system. The possibility of the formation of solid solutions of methane in propane hydrates and of propane in methane hydrates existing under different P–T conditions is discussed on the basis of P–T curves corresponding to monovariant equilibria in the system.

Double Gas Hydrates at High Pressures: The Highest Decomposition Temperatures

Abstract: CS‐II double clathrate hydrates of tetrahydrofuran, CHCl3, CCl4, SF6, and xenon as a “help gas” keep their structures in the pressure interval 1215,000 bar. Decomposition temperatures of these hydrates rise monotonically in the pressure interval under consideration. The decomposition temperature of the double clathrate hydrate of SF 6 and xenon reaches 129.48C at 14.8 kbar.