| ΑW|L@½Ζ³Ν| Rev. High Pressure Sci. Technol. 8-2,86-95(1998) |
| Theoretical Models in High Pressure Reaction Kinetics: from Empirical Correlations to Molecular Dynamics |
| N. Weinberg |
| A variety of theoretical methods is currently available for the analysis of the effects of high pressures on reaction kinetics, ranging from simple empirical correlations to sophisticated molecular dynamics simulations. Most of them operate within the framework of the transition state theory where the concept of activation volume naturally emerges as the pressure derivative of the activation Gibbs energy. Different models of activation volumes are discussed, as well as the effects of high pressures on reaction profiles, temperature-dependent effects of high pressures, and effects of equilibrium and nonequilibrium solvation. [high pressure kinetics, activation volume, reaction profile, solvent effect, nonequilibrium solvation] |
| Department of Chemistry, University College of the Fraser Valley, Abbotsford, BC, V2S 7M9, Canada and Department of Chemistry, Simon Fraser University, Burnaby, BC, V5A 1S6, Canada |
| ΑW|L@½Ζ³Ν| Rev. High Pressure Sci. Technol. 8-2,96-103(1998) |
| Molecular Theories of Partial Molar Volume |
| F. Hirata1,2, T. Imai2 , and M. Irisa3 |
| Two main streams in the molecular theories for partial molar volume are reviewed. The first stream is based on the scaled particle theory of liquids and its extension to polyatomic molecules; This has been used successfully in determining the solvation free energy of non-polar solutes in water. The second method employs the Kirkwood-Buff solution theory. This method is coupled to the integral equation theory of molecular liquids to calculate the partial molar volume of polyatomic molecules. The dependence of the partial molar volume on conformational change of butane and a tripeptide is examined based on the methods. [partial molar volume, scaled particle theory, Kirkwood-Buff theory, RISM theory, butane, peptide, water] |
| 1 Department of Theoretical Study, Institute for Molecular Science, 38 Nishigonaka, Myodaiji, Okazaki 444-8585 2 Department of Functional Molecular Science, The Graduate University for Advanced Studies, 38 Nishigonaka, Myodaiji, Okazaki 444-8585 3 Faculty of Computer Science and Engineering, Kyushu Institute of Technology, 680-4 Kawazu Iizuka 820-8502 |
| ΑW|L@½Ζ³Ν| Rev. High Pressure Sci. Technol. 8-2,104-110(1998) |
| Organic Reactions at High Pressure |
| Frank-Gerrit Klarner* and Frank Wurche* |
| The utility of high pressure for the understanding of chemical reactions and its applications in organic synthesis is demonstrated for pericyclic reactions (cycloadditions, Cope rearrangements, electrocyclizations and intramolecular Diels-Alder reactions). With the example of the peptide coupling it is shown that pressure is a valuable tool for the control of other reactions than pericyclic reactions, too. [Cycloadditions, packing coefficients, product selectivity, supramolecules, thermally labile compounds, peptide coupling] |
| Institut fur Organische Chemie, Universität GH Essen. Universitätsstr, 5,D-45117 Essen, Federal Repabric of Germany |
| ΑW|L@½Ζ³Ν| Rev. High Pressure Sci. Technol. 8-2,111-120(1998) |
| High Pressure - a Useful Parameter for Catalysis? |
| Oliver Reiser |
| The scope and limitation of high pressure for the catalysis of organic reactions is evaluated. This article focuses on Lewis acid (cycloadditions, epoxide openings, Horner-Wadsworth-Emmons reactions) and palladium catalyzed (Heck-reaction, [3+2] cycloadditions) reactions. Aspects of reactivity (turnover frequencies and turnover rates) as well as selectivity (chemoselectivity, regioselectivity, diastereo- and enantioselectivity) under the influence of pressure will be discussed. [catalysis, organic reaction, cycloaddition, Lewis acid, palladium, Heck-reaction, alkenylation] |
| Institut fúr Organische Chemie, Universität Regensburg, Universität sstr. 31, 93053 Regensburg, Germany. e-mail: Oliver.Reiser@chemie.uni-regensburg.de |
| _Ά Rev. High Pressure Sci. Technol. 8-2,121-123(1998) |
| Raman Studies on Solid CO2 and N2 with Excess He at Pressures up to 40 GPa |
| A. P. Jephcoat and H. Olijnyk |
| Raman spectra of CO2 and the van-der-Waals ccompound He(N2)11 were obteined rnder nearly hydrosstatic pressures up to 40 GPa. The pressure induced changes of the librational spectra suggest thea solid CO2 does not transform directly from phase-1 (cubic Pa3) to phase-III(orthorhombic Cmca). An intermediate phase-IV. which my involve onlly minor modifications of phase-I. is formed prior to the traansition to Cmca structure. Phase IV and III coexist over some present range. The pressure shifts of all four Raman active librons of phase-III were determined over a wide pressure raange and are compared to previous theoretical results. Spectra of external and internal modes the van-der-Waals compound He(N2)II are very similar to those of e-N2 and imply a clise relationship between the structures of He(N2)II and e-N2 . The observed splitting of the main vibron of iisotooic species 14N-15N indicates that in addition to factor-grooup interactions site effects are responsible for the observed splittings of the 14N2 main vibron of He(N2)II. [molecular crystals, vibrational spectroscopy, high pressure, Phase transitions] |
| Department of Earth sciences, University of Oxford, Oxford, OXI 3PR, UK |
| ΐ±|Cg Rev. High Pressure Sci. Technol. 8-2,124-126(1998) |
| OpX[Uπp’½ΕΜΜSjIvͺ(XΞΎ@)ΜΈx» High Time-Resolved Hugoniot Measurement by the Inclined-Mirror Method@using a Long-Pulsed Laser |
| ΰμ³a*C^Ί@Ξ Masakazu UCHINO Tsutomu MASHIMO |
| We produced a long-pulsed dye laser with no Q-switch for the shock-wave measurement or time-resolved spectroscopy under shock compression of solids. The average output power of this laser was larger than 13 kW (effective pulse duration ; `50 µs). This laser has been used as a light source for the Hugoniot measurement of solids by the inclined-mirror method combined with a rotating-mirror type streak camera. It was confirmed that the time resolution of Hugoniot measurement increased to higher than 1 ns. [long-pulsed laser, shock compression, Hugoniot measurement, inclined-mirror method] |
| §860-8555@F{s―2-39-1 F{εwHwΥGlM[ΐ± High Energy Rate Laboratory, Faculty of Engineering, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555. *»§807 -0831@kγBsͺ¦Όζ₯Ό3-6-1 ͺ§HΖZpZ^[@Bdq€ Fukuoka Industrial Technology Centor, 3-6-1 Norimatsu, Yahatanishi-ku, Kitakyusyu, Fukuoka 807-0831. |
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