Compressed-tube pressure cell for optical studies at ocean pressures: Application to glucose mutarotation kinetics.

A self-contained compressed-tube pressure cell is tested to 25 MPa. The cell is very simple to construct and offers stable pressure control with optical access to fluid samples. The physical path length of light through the cell is large enough to measure optical activity. The entire system is relatively small and portable, and it is vibration-free, since a compressor is not used. Operation of the cell is demonstrated by measuring the mutarotation rate of aqueous glucose solutions at 25 °C. A logarithmic plot of the rate constant vs. pressure yields an activation volume for mutarotation of -22 cm3/mol, approximately twice the value measured previously at higher pressures.

Index of refraction, density, and solubility of ammonium iodide solutions at high pressure.

An asymmetric moissanite anvil cell is used to study aqueous solutions of ammonium iodide at pressures up to 10 kbar. The index of refraction is measured using the rotating Fabry-Perot technique, with an accuracy of approximately 1%. The mass density and molar volume of the solutions are estimated using the measured index values, and the molar volume is used to predict the pressure dependence of the solubility. The solubility derived from the index of refraction measurements is shown to agree with that which is determined by direct observation of the onset of crystallization.

Raman and X-ray scattering studies of high-pressure phases of urea.

Single-crystal and polycrystalline urea samples were compressed to 12 GPa in a diamond-anvil cell. Raman-scattering measurements indicate a sequence of four structural phases occurring over this pressure range at room temperature. The transitions to the high-pressure phases take place at pressures near 0.5 GPa (phase I --> II), 5.0 GPa (II --> III), and 8.0 GPa (III --> IV). Lattice parameters in phase I (tetragonal, with 2 molecules per unit cell, space group P42(1)m (D3(2d))) and phase II (orthorhombic, 4 molecules per unit cell, space group P2(1)2(1)2(1) (D2(4))) were determined using angle-dispersive X-ray diffraction experiments. For phases III and IV, the combined Raman and diffraction data indicate that the unit cells are likely orthorhombic with four molecules per unit cell. Spatially resolved Raman measurements on single-crystal samples in phases III and IV reveal the coexistence of two domains with distinct spectral features. Physical origins of the spatial domains in phases III and IV are examined and discussed.