High pressures phases

Doverspike M A, Liu S B, Ennis P, Johnson T, Conrad M S, Luszczynski Kand Norberg R E 1986 NMR in high-pressure phases of solid ammonia and ammonia-d, Phys. Rev. B 33 14... 

Except for helium, all of the elements in Group 18 free2e into a face-centered cubic (fee) crystal stmeture at normal pressure. Both helium isotopes assume this stmeture only at high pressures. The formation of a high pressure phase of soHd xenon having electrical conductivity comparable to a metal has been reported at 33 GPa (330 kbar) and 32 K, and similar transformations by a band-overlap process have been predicted at 15 GPa (150 kbar) for radon and at 60 GPa (600 kbar) for krypton (51). 

In addition to the three principal polymorphs of siUca, three high pressure phases have been prepared keatite [17679-64-0] coesite, and stishovite. The pressure—temperature diagram in Figure 5 shows the approximate stabiUty relationships of coesite, quart2, tridymite, and cristobaUte. A number of other phases, eg, siUca O, siUca X, sihcaUte, and a cubic form derived from the mineral melanophlogite, have been identified (9), along with a stmcturaHy unique fibrous form, siUca W. 

R. J. Sadus, High Pressure Phase Behaviour of Multicomponent Fluid Mixtures, Elsevier, Amsterdam, the Netherlands, 1992. 

Figure 4.12. Shock velocity versus particle velocity for fused quartz. Three regimes are indicated low pressure, fused quartz regime, the mixed phase regime, and the high-pressure phase, stishovite regime.

Figure 4.15. Shock pressure versus specific volume for calcia and fused quartz indicating three regimes fused quartz, low-pressure regime is fused quartz, mixed phase regime, and high-pressure regime representing stishovite. In the case of calcia, the low-pressure phase is the B1 structure, mixed phase is indicated, and the high-pressure phase regime is in the B2 structure.

Figure 4.28. Measured and calculated shock temperatures versus pressure for for-sterite for low-pressure (olivine), mixed phase, and high-pressure phase regime (possibly MgO periclase) -I- MgSi03 (perovskite)). Shock temperatures in the mixed phase regime (Ahrens et al., 1969).

In 1963, McQueen, Fritz, and Marsh (J. Geophys. Res. 68, p. 2319) suggested that the high-pressure shock-wave data for fused quartz (Table 1) and the data for crystal quartz pg = 2.65 g/cm, Co = 1.74 km/s and s = 1.70, both described the shock-induced high-pressure phase of SiOj, stishovite pg = 4.35 g/cm ), above 50 GPa. Assume Ej-j, = 1.5 kJ/g show that these shock data are consistent with a constant value of y = 0.9 in the 50-100 GPa range. 

Ahrens, T.J., Anderson, D.L., and Ringwood, A.E. (1969), Equation of State and Crystal Structures of High-Pressure Phases of Shocked Silicates and Oxides, Rev. Geophys. 7, 667-707. 

When the temperature or pressure is decreased very rapidly, high temperature or high pressure phases can be "trapped", and are observed at atmospheric temperature and pressure (diamond, for instance, is a high-pressure form of carbon. It is only metastable at atmospheric pressure the stable form is graphite.)... 

On the other hand, the formation of the high pressure phase is preceded by the passage of the first plastic wave. Its shock front is a surface on which point, linear and two-dimensional defects, which become crystallization centers at super-critical pressures, are produced in abundance. Apparently, the phase transitions in shock waves are always similar in type to martensite transitions. The rapid transition of one type of lattice into another is facilitated by nondilTusion martensite rearrangements they are based on the cooperative motion of many atoms to small distances. ... 

The room temperature transformation of the columbite phase to baddeleyite commences at 13-17 GPa 6, with transition pressure increasing linearly with temperature Direct transition from rutile to baddeleyite phase at room temperature and 12 GPa has also been reported 7. The baddeleyite phase undergoes further transition to an as yet undefined high-symmetry structure at 70-80 GPa. The most likely candidate for the high-pressure phase is fluorite, which is consistent with the general pattern of increasing Ti coordination number from 6 in rutile, to 7 in baddeleyite (a distorted fluorite structure), and to 8 in fluorite. 

J. Tang and S. Endo, P-T boundary of a-Pb02 type and baddeleyite type high-pressure phases of titanium... 

P.Y. Simons and F. Dachille, The structure of Ti02 II, a high-pressure phase of Ti02, Acta Crysi. 

V.I. Smelyansky and J.S. Tse, Theoretic study of the high-pressure phase transformation in ZnSe,... 

Takemura and co-workers31 have shown by optical measurements, X-ray diffraction and micro-DTA measurements that the high-pressure phase is liquid-crystalline, and that... 

Vapor-phase fugacity coefficients are needed not only in high-pressure phase equilibria, but are also of interest in high-pressure chemical equilibria (D6, K7, S4). The equilibrium yield of a chemical reaction can sometimes be strongly influenced by vapor-phase nonideality, especially if reactants and products have small concentrations due to the presence in excess of a suitably chosen nonreactive gaseous solvent (S4). 

Chueh s method for calculating partial molar volumes is readily generalized to liquid mixtures containing more than two components. Required parameters are and flb (see Table II), the acentric factor, the critical temperature and critical pressure for each component, and a characteristic binary constant ktj (see Table I) for each possible unlike pair in the mixture. At present, this method is restricted to saturated liquid solutions for very precise work in high-pressure thermodynamics, it is also necessary to know how partial molar volumes vary with pressure at constant temperature and composition. An extension of Chueh s treatment may eventually provide estimates of partial compressibilities, but in view of the many uncertainties in our present knowledge of high-pressure phase equilibria, such an extension is not likely to be of major importance for some time. 

With a suitable equation of state, all the fugacities in each phase can be found from Eq. (6), and the equation of state itself is substituted into the equilibrium relations Eq. (67) and (68). For an A-component system, it is then necessary to solve simultaneously N + 2 equations of equilibrium. While this is a formidable calculation even for small values of N, modern computers have made such calculations a realistic possibility. The major difficulty of this procedure lies not in computational problems, but in our inability to write for mixtures a single equation of state which remains accurate over a density range that includes the liquid phase. As a result, phase-equilibrium calculations based exclusively on equations of state do not appear promising for high-pressure phase equilibria, except perhaps for certain restricted mixtures consisting of chemically similar components. 

While the dilated van Laar model gives a reliable representation of constant-pressure activity coefficients for nonpolar systems, the good agreement between calculated and experimental high-pressure phase behavior shown in Fig. 14 is primarily a result of good representation of the partial molar volumes, as discussed in Section IV. The essential part of any thermodynamic description of high-pressure vapor-liquid equilibria must depend,... 

Abstract Molecular spectroscopy is one of the most important means to characterize the various species in solid, hquid and gaseous elemental sulfur. In this chapter the vibrational, UV-Vis and mass spectra of sulfur molecules with between 2 and 20 atoms are critically reviewed together with the spectra of liquid sulfur and of solid allotropes including polymeric and high-pressure phases. In particular, low temperature Raman spectroscopy is a suitable technique to identify single species in mixtures. In mass spectra cluster cations with up to 56 atoms have been observed but fragmentation processes cause serious difficulties. The UV-Vis spectra of S4 are reassigned. The modern XANES spectroscopy has just started to be applied to sulfur allotropes and other sulfur compounds. 

Since the vibrational spectra of sulfur allotropes are characteristic for their molecular and crystalline structure, vibrational spectroscopy has become a valuable tool in structural studies besides X-ray diffraction techniques. In particular, Raman spectroscopy on sulfur samples at high pressures is much easier to perform than IR spectroscopical studies due to technical demands (e.g., throughput of the IR beam, spectral range in the far-infrared). On the other hand, application of laser radiation for exciting the Raman spectrum may cause photo-induced structural changes. High-pressure phase transitions and structures of elemental sulfur at high pressures were already discussed in [1]. 

ArV is not necessarily positive, and to compare the relative stability of the different modifications of a ternary compound like AGSiOs the volume of formation of the ternary oxide from the binary constituent oxides is considered for convenience. The pressure dependence of the Gibbs energies of formation from the binary constituent oxides of kyanite, sillimanite and andalusite polymorphs of A SiOs are shown in Figure 1.10. Whereas sillimanite and andalusite have positive volumes of formation and are destabilized by pressure relative to the binary oxides, kyanite has a negative volume of formation and becomes the stable high-pressure phase. The thermodynamic data used in the calculations are given in Table 1.7 [3].1... 

More recent quantum-based MD simulations were performed at temperatures up to 2000 K and pressures up to 30 GPa.73,74 Under these conditions, it was found that the molecular ions H30+ and OH are the major charge carriers in a fluid phase, in contrast to the bcc crystal predicted for the superionic phase. The fluid high-pressure phase has been confirmed by X-ray diffraction results of water melting at ca. 1000 K and up to 40 GPa of pressure.66,75,76 In addition, extrapolations of the proton diffusion constant of ice into the superionic region were found to be far lower than a commonly used criterion for superionic phases of 10 4cm2/s.77 A great need exists for additional work to resolve the apparently conflicting data. 

High pressure phase (p > 3GPa) modified A1B2 type [4]... 

Liu, L.-G. and Bassett, W.A. (1986) Elements, Oxides, and Silicates - High Pressure Phases with Implications for the Earth s Interior, Oxford Monographs on Geology and Geophysics, N.4 (Oxford University Press, New York). 

---