Gas hydrates of nitrogen and oxygen are described. P -t relations of the three-phase equilibria in the system nitrogen -water are given from -4 to 18°C at pressures up to 1000 atm.The dissociation pressure of oxygen hydrate is given at 0°C.In the late 19th century many solid gas hydrates were described, especially by Villard and De Forcrand 1. Usually these hydrates have low solubility in water. A great increase in pressure is required for these hydrates to persist at increasing temperature.Furthermore, the following relation generally holds : "The lower the boiling point of the hydrate-forming gas, the higher the equilibrium pressure".The most unstable hydrate known so far was reported by Villard in 1896 ; it was argon hydrate, having an equilibrium pressure at 0°C of about 100 atm.Hydrates of the gases He, Hz, Ne, N2, CO, 0 2 , and NO have not been described, although Villard indeed searched for these compounds 1.The availability of a high-pressure apparatus for pressures up to 1000 atm, recently developed in our laboratory 2, has induced a reinvestigation.We have been aided in this by the theoretical calculations of Platteeuw and van der Waals, who expected the equilibrium pressure of N2 and 0 2 hydrate at 0°C to be 90 and 63 atm. respectively 3.Our experiments have actually led to the discovery of the hydrates of NZ and 0 2 , a result which makes us hope that the hydrates of CO and NO will also be found to exist.The apparatus, described in detail in 2, consists of an autoclave of
p-t relations of different three phase equilibria in the systems nitrogen-water and oxygen-water are given from -6 to 18" for pressures up to 10o0 atm. From the data, the heats of formation of nitrogen-and oxygen-hydrate and the composition of these hydrates were calculated.
The P-t projection of the three phase equilibrium, hydrateliquidgas, up to pressures of 10oO atm is recorded. An explanation is given for the sharp rise occurring at -18" in the slope of the three phase curve HLG.
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