Phase equilibria in the system CO2-H2O I: New equilibrium relations at low temperatures

Graphical analysis of free-energy relationships involving binary quadruple points and their associated univariant equilibria in the system CO₂-H₂O suggests the presence of at least 2 previously unrecognized quadruple points and a degenerate binary invariant point involving an azeotrope between CO₂-rich gas and liquid. Thermodynamic data extracted from the equilibrium involving clathrate (hydrate), gas, and ice (H = G+I) are employed along with published data to calculate the P-T range of the 3-ice equilibrium curve, S+I = H, where S is solid CO₂. This equilibrium curve intersects the H = G+I curve approximately where the latter curve intersects the S+H = G curve, thus confirming the existence of one of the inferred quadruple points involving the phases S, G, H, and I. Recognition of some binary equilibria probably have been hampered by extremely low mutual solubilities of CO₂ and H₂O in the fluids phases which, for example, render the S+H = G virtually indistinguishable from the CO₂-sublimation curve.To make the published portion of the L(liquid CO₂)-G-H equilibrium “connect” with the other new quadruple point involving S, L, G, and H, it is necessary to change the sense of the equilibrium from L = G+H at higher pressures to L+H = G at lower pressures by positing a L = G azeotrope at very low concentrations of H₂O. At the low-pressure origin of the azeotrope, which is only a few bars above the CO₂-triple point, the azeotrope curve intersects the 3-phase curve tangentially, creating a degenerate invariant point at which the 3-phase equilibrium changes from L+H = G at lower pressures to L = G+H at higher pressures. The azeotrope curve is offset at slightly lower temperature from the L = G+H curve until the 3-phase equilibrium terminates at the quadruple point involving G, L, H, and W (water). With further increase in pressure the azeotrope curve tracks the L = G+W equilibrium and apparently terminates at a critical end point in close proximity to critical endpoints for the CO₂-saturation curve and the L = G+W curve.Thermodynamic data for clathrate extracted from the slope of the H = G+I curve are consistent with a solid-state phase transformation in CO₂-clathrate between 235 and 255 K. Published work shows that the type-I clathrate phase, whose atomic structure is a framework of water molecules with CO₂ molecules situated in large “guest” sites within the framework, is variable in composition with ∼1 guest site vacancy per unit cell at the high-temperature limit of its stability; the number of water molecules, however, remains constant. The formula (CO₂)_8-y·46H₂O, where y is the number of vacancies per unit cell, is in keeping with the atomic structure, whereas the traditional formula, CO₂·nH₂O, where n (hydration number) = 5.75, is misleading.Ambient P-T conditions in the Antarctic and Greenland ice sheets are compatible with sequestering large amounts of carbon as liquid CO₂ and/or clathrate.