High pressure differential thermal analysis of nematic compounds with different molecular shapes

By means of high pressure differential thermal analysis we measured the pressure/temperature phase diagrams of several nematic compounds with different molecular structures. Using pressures up to about 500 M Pa we found strongly nonlinear clearing curves. This behaviour is interpreted as changes from 'weak' intermolecular potentials to 'hard' potentials, or using thermodynarmic arguments, strong pressure dependence of the volume discontinuity at the clearing transitions.     

Di[2-(4-substituted-phenyl)-3-mercapto-propenato]-nickel(II) complexes. Metallo-mesogens exhibiting broad nematic ranges

Di[2-(4-substituted-phenyl)-3-mercapto-propenato]-nickel(II) complexes have been synthesized and investigated. All of them are mesomorphic; they have nematic phases with wide ranges and typical Schlieren textures.     

Photoinduced electron transfer variables: rigidity or orientation?

The relatives photoreactives of bridged-ring systems 1, 3, 5-X and 6-X (X ≡ Cl or Br) have been studied at 254 nm in acetic acid. The formation of photosolvolysis product was rationalized in terms of photoinduced intramolecular electron transfer (ET) processes. The relative ease of ET in these donor—bridge—acceptor model system was analyzed in terms of known ET variables including free-energy changes, orientation effects and ridigity effects. The observed relative photoreactivities agreed better with the calculated free-energy changes when relative rigidities of the electron acceptor termini were evaluated. In general, the more rigid system were more photoreactive.     

Pressure-induced dislocation amorphization of crystals

In terms of the isotropic elastic crystal model, it is shown that the formation of planar layers consisting of edge dislocation pileups is advantageous in energy if the shear modulus of the crystal is far lower than the bulk modulus. As pressure rises, the dislocation radius decreases, which can destroy the crystal structure.     

Model calculations of interface segregation in dilute systems

Using a discrete model for the segregation kinetics based on the Darken theory of diffusion and on the regular solution model (RSM), one and two dimensional simulations of interface segregation in binary and ternary systems have been performed. The aim of the calculations was to investigate the kinetics of segregation sequences in ternary systems, the segregation kinetics in discrete systems during the initial phase and finally the kinetics of surface segregation in the region of a grain boundary intersected by the surface.     

Resonance ionization spectroscopy for trace analysis and fundamental research

Resonance ionization spectroscopy (RIS) and its combination with mass spectrometry (RIMS) have grown to become powerful techniques, which offer high sensitivity as well as elemental and isotopic selectivity. The principles of RIS and RIMS are introduced; they primarily concern the analysis of the optical spectra for the choice of efficient excitation schemes and the suitable design of the experimental apparatus. Recent applications span from studies of short-lived isotopes at on-line mass separators to a wide variety of trace analysis applications for radioactive isotopes, which can range from measurements of solar neutrino flux to environmental assessment.On leave from Pacific Northwest Laboratory, Richland, USA     

Kinetics of solvolysis of 2-chloroquinoxaline

Pseudo-first-order rate constants and activation parameters have been measured for the solvolysis of 2-chloroquinoxaline in various aquo-organic mixtures using methanol, ethanol, and isopropanol as the organic solvent. Excellent linear correlations are found between lnk and the mol fraction of cosolvent and ln[H₂O]. The medium effect on the rates of solvolysis is assessed by Grunwald–Winstein's mY correlationship. The estimated values of m (0.55–0.72) and the entropy of activation (148–212 J deg^?1 mol^?1) for the reactions are well in the range for a bimolecular aromatic substitution reactions. © 1994 John Wiley & Sons, Inc.     

Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in the gas phase

The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (ACDP) in the presence of n-octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first-order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six-fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k₁/(s^?1) = (31.8 ± 2.5) ? [(39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one O? O bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc.