High-pressure bulk synthesis of crystalline C(6)N(9)H(3).HCl: a novel c(3)n(4) graphitic derivative.

A novel carbon nitride compound, structurally related to the proposed graphitic phase of C(3)N(4), has been synthesized in a bulk well-crystallized form. The new material, with stoichiometry C(6)N(9)H(4)Cl, was prepared through a solid-state reaction of 2,4,6-triamino-1,3,5-triazine with 2,4,6-trichloro-1,3,5-triazine at 1.0-1.5 GPa and 500-550 degrees C and also through a self-reaction of 2-amino-4,6-dichloro-1,3,5-triazine at similar conditions. X-ray and electron diffraction measurements on the yellowish compound indicate a hexagonal space group (P6(3)/m) with cell parameters of a = 8.4379(10) A and c = 6.4296(2) A. This new compound possesses a two-dimensional C(6)N(9)H(3) framework that is structurally related to the hypothetical P6m2 graphitic phase of C(3)N(4), but with an ordered arrangement of C(3)N(3) voids. The large voids in the graphene sheets are occupied by chloride ions with an equivalent number of nitrogen atoms on the framework protonated for charge balance. The composition of the sample was determined by bulk chemical analysis and confirmed by electron energy loss (EELS) spectroscopy. The chemical and structural model is consistent with bulk density measurements and with the infrared and (13)C NMR spectra. This work represents the first bulk synthesis of a well-characterized and highly crystalline material containing a continuous network of alternating carbon and nitrogen atoms.

Liquids at large negative pressures: water at the homogeneous nucleation limit.

An isochoric cooling method for obtaining unprecedented tensions on liquids was used to determine the homogeneous nucleation limit for stretching of water at a variety of water densities. At densities in the range 0.55 to 0.68 gram per milliliter (g/ml), the data agree with the homogeneous nucleation temperatures measured by Skripov for superheated water at positive pressures. At densities between 0.68 and 0.93 g/ml, cavitation occurred only at negative pressures (that is, under tension). The cavitation tensions measured were in excellent agreement with those predicted by Fisher's 1948 vapor nucleation theory. A maximum tension of 140 megapascals (=1400 bars) was reached at 42 degrees C, which lies on an extrapolation of the line of isobaric density maxima. At higher densities, cavitation of droplets that survived heterogeneous nucleation failed to occur at all unless provoked, at much lower temperatures, by freezing. This observation confirms the existence of a density maximum at 42 degrees C and -140 megapascals and hence greatly strengthens the basis for Speedy's conjecture of a reentrant spinodal for water.

Water and solutions at negative pressure: Raman spectroscopic study to -80 megapascals.

Microscopic inclusions of aqueous fluids trapped in interstices in quartz and other crystals provide novel systems for the deliberate study of liquids under tension. Liquids under tension should differ in interesting ways from those at ambient pressure or compressed liquids because attractive, rather than repulsive, forces should dominate their behavior. Static tensions in excess of 100 megapascals (~1000 atmospheres) have been obtained reproducibly. Video-recorded observations of the final liquid rupture process, coupled with extrapolations of data at positive pressure, suggest that the homogeneous vapor nucleation point was reached in two of the cases studied. Raman spectra of the fluids at -80 megapascals show that an isothermal volume stretch of -5 percent by volume has only a weak effect on the spectral features and is similar to the effect of isobaric heating.