Rev. High Pressure Sci. Technol.

Vol.2  No.2(1993) Abstract

Rev. High Pressure Sci. Technol. 2-2,93-96(1993)
High Pressure and Organic Reactions
中原 勝
In this review, we outline the general aspects of the effect of pressure on chemical reactions and related phenomena in the condensed phases. To make it clear to what extent the high pressure study has been developed in this field, we look back the situation of the 1920's. It is illustrated here how useful high pressure is for testing theoretical models for chemical reaction dynamics, elucidating the mechanism of chemical and biological reaction processes, synthesizing new materials, and developing new technologies for processing foods and hazardous materials. Main Problems concerning the theoretical models for the rate constant in the liquid phase are summarized.
〒611-0011 宇治市五ヶ庄 京都大学化学研究所
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011

Rev. High Pressure Sci. Technol. 2-2,97-102(1993)
Application of High Pressures to Organic Synthesis
佐々木伸樹 山本嘉則
Nobuki SASAKI Yoshinori YAMAMOTO
Recent progress on the high pressure mediated organic synthesis is summarized. Substitution reactions of a alcohols, hydrolysis of esters, SNAr reactions, and some organometallic reactions are accelerated by high pressure.
東北大学理学部化学教室 Department of Chemistry, Faculty of Science, Tohoku University
〒980 仙台市青葉区荒巻字青葉 Aramaki, Aoba, Aoba-ku, Sendai 980

Rev. High Pressure Sci. Technol. 2-2,103-109(1993)
Recent Progress in Organic Synthesis under High Pressure
飯田博一A 内田高峰B 松本澄A
Hirokazu IIDA Takane UCHIDA Kiyoshi MATSUMOTO
The high pressure apparatus are now only moderately expensive, and can be employed, usefully and without much extra effort, in a much wide context than that originally envisaged. This article deals with the recent developments made in such fields as 1)Diels-Alder reaction, 2)1,3-dipolar reaction, 3)nucleophilic substitution, 4)Mannich reaction.
Graduate School of Human and Environmental Studies, Kyoto University
〒606-8501 京都市左京区吉田近衛町 Yoshidakonoe-cho, Sakyo-ku, Kyoto 606-8501
B福井大学教育学部 Faculty of Education, Fukui University
〒910 福井市文京 Bunkyo, Fukui 910

Rev. High Pressure Sci. Technol. 2-2,110-118(1993)
Dynamic Solvent Effects on Photoisomerizations at High Pressures
原 公彦
Kimihiko HARA
Photoisomerization reactions, which usually involve large amplitude motion of a bulky group twisting around a molecular axis, are often used to test theories of dynamic solvent effects, since the rate of isomerization depends critically on the frictional forces exerted by the solvent molecules. The photoreaction can be initiated with a short pulse of light, and their progress can be monitored by similarly fast time-resolved techniques. The experimental results of the solvent viscosity effect have been analyzed in terms of the Kramers theory or its extended theories developed more recently. In this article the theoretical implication of the dynamic solvent effect is briefly looked into, and it's application to some recent experimental results for photoisomerization reactions studied by high-pressure method is reviewed.
京都大学理学部化学科 Department of Chemistry, Faculty of Science, Kyoto University
〒606-8502 京都市左京区北白川 Kitashirakawa, Sakyo-ku, Kyoto 606-8502

Rev. High Pressure Sci. Technol. 2-2,119-124(1993)
Viscosity Effect on the Fast Reaction in Solution
Viscosity effect through high pressure on the fast bimolecular reaction involved in the photochemical processes in solution has been reviewed; the systems selected in this article are (1)excimer and exciplex formation reactions, (2)cycloaddition reactions between singlet oxygen and furans, and (3)singlet and triplet quenching by molecular oxygen of anthracene derivatives. For these systems, the contribution by diffusion to the reactions is described.
京都工芸繊維大学 Faculty of Engineering and Design, Kyoto Institute of Technology
〒606-8585 京都市左京区松ヶ崎 Matsugasaki, Sakyo-ku, Kyoto 606-8585

Rev. High Pressure Sci. Technol. 2-2,125-131(1993)
Effect of Solvent Viscosity on Slow Thermal Isomerizations
Tsutomu ASANO
This article presents the results of high-pressure kinetic study of slow thermal isomerizations (eq.1) in viscous solvents. The results clearly demonstrated that the analysis based on the transition state theory (TST) becomes invalid only under extremely viscous conditions. By inserting the observed rate constants and the extrapolated TST-expected rate constants to eq.2, diffusion-limited rate constants kdif were estimated. The values thus obtained gave linear Arrhenius plots suggesting the present reactions proceed via two-step mechanism, namely, a diffusion-limited rate process followed by an activation-limited one.
大分大学工学部 Faculty of Engineering, Oita University
〒870-1192 大分市旦野原700 700 Tannohru, Oita 870-1192

Rev. High Pressure Sci. Technol. 2-2,132-138(1993)
High-Pressure, High-Resolution NMR
Hiroaki YAMADA
The high-pressure, high-resolution nuclear magnetic resonance (HPHR-NMR) spectroscopy represents one of the most important and indispensable tools for studying high-pressure chemistry, biochemistry, and physics at the atomic and molecular level. After reviewing briefly the advances in HPHR-NMR, I describe in detail the two types of pressure-resisting glass cell techniques for HPHR-NMR, and provide some examples of the experimental application of these handy-type devices to studies of pressure-induced structural changes in simple organic molecules.
神戸大学理学部化学教室 Department of Chemistry, Faculty of Science, Kobe University
〒657 神戸市灘区六甲台町 Rokkodai-cho, Nada-ku, Kobe 657

Rev. High Pressure Sci. Technol. 2-2,139-145(1993)
High Pressure Electron Spin Resonance of Radicals in Solution
末石芳巳 西村範生
The history of high-pressure ESR techniques applied to solution chemistry has been surveyed briefly, and our recent investigations have been reviewed. The results are summarized as follows: (1)The rate of spin exchange reactions of nitroxides is diffusion-controlled, and the activation volume is closely related to that for diffusive processes. (2)The rates of spin-lattice relaxation for the photo-reduced products of 2,5-di-tert-butyl-1,4-benzoquinone(2,5-DBQ) were estimated at various pressures. (3)From the pressure effects on the ESR signal, aspects of di-tert-butyl nitroxide(DTBN) included in cyclodextrins were inferred. (4)The information on the rotational motion of spin-labeled long-chain molecules in solutions was obtained from the anisotropic ESR signals.
岡山大学理学部 Department of Chemistry, Faculty of Science, Okayama University
〒700 岡山市津島中3-1-1 3-1-1 Tsushima Naka, Okayama 700

Rev. High Pressure Sci. Technol. 2-2,146-150(1993)
A Trend of the Measurements of High Pressure
山本 昇次郎
A trend of measurements of high pressure with an accuracy of better than ±0.1% in the range up to 1 GPa is described. The instruments used are the dead-weight piston manometer, the manganin resistance manometer and strain-gauge type pressure transducer. The piston manometers are available commertially with an accuracy of ±0.01%. The secondary instruments should be calibrated against the primary but have become very convenient to use due to the progress of the digital electronic indicator.
Mechanical Metrology Department, National Research Laboratory of Metrology
〒305 つくば市梅園1-1-4 Umezono, Tsukuba 305

Rev. High Pressure Sci. Technol. 2-2,151-160(1993)
Mechanism of Deep-Focus Earthquakes Inferred from High Pressure Experiments
島田 充彦
Mitsuhiko SHIMADA
Deep-focus earthquakes occur at depths from the earth's surface up to 680 km (corresponding to pressure of 24 GPa). They occur only in the restricted areas in the earth, or the subduction zones. There have been many studies on the nature of the deep-focus earthquakes, but they have not been widely accepted since each model has both advantage and disadvantage to explain the observation facts and the physical, chemical, chemical and mechanical properties of rocks and minerals. Recently, two new models are proposed based on the high pressure experiments, together with our understanding of the structure of the subduction zone. One is the transformation faulting (or anticrack faulting) model, and the other is the amorphization model. In this article, these new models inferred from high pressure experiments are reviewed with the brief history of the finding of deep-focus earthquakes and of the studies of their mechanism.
Research Center for Earthquake Prediction, Disaster Prevention Research Institute, Kyoto University
〒611-0011 宇治市五ヶ庄 Uji 611-0011

Rev. High Pressure Sci. Technol. 2-2,161-166(1993)
Application of Hot Isostatic Pressing-Ceramic Cutting Tools-
古川 満彦
Mitsuhiko FURUKAWA
The application of HIP(hot isostatic pressing) technology to cutting tools began with high-speed steels at the end of the 1960s, followed by cemented carbide sintered bodies in 1970. In 1977, HIP technology was used in Japan in the mass production of alumina ceramic cutting tools, for the first time in the world.
Ceramic cutting tools require high fracture toughness. The introduction of HIP technology into the manufacturing process has enhanced materials strength and fracture toughness by enabling the production of ceramic materials with finer and more uniform grain.
Hot isostatic pressing is unquestionably one of the most important processes for the production of ceramic cutting tools.
日本タングステン(株)研究開発部 Nippon Tungsten Co., LTD.
〒815 福岡市南区清水2丁目20番31号 20-31, Shimizu 2-chome, Minami-ku, Fukuoka 815

Rev. High Pressure Sci. Technol. 2-2,167-170(1993)
Anecdote of the Diamond Synthesis (4)
"Challenges to larger high-pressure volume designs"
細見 暁
Ishizuka's designs with the characteristic use of a hard sintered alumina cylinder permitted to replace the conventional die material of tungsten carbide with steels which were more ready for the construction of larger components. Thus larger apparatuses were built for the diamond production with a 7000-ton hydraulic press. The most urgent problem in the operation was how to prepare cylinders fast enough to keep pace with the scheduled production.
トーメイダイヤ(株) Tomei Diamond Co., LTD.
〒323-0807 栃木県小山市城東4-5-1 4-5-1 Joto, Oyama 323-0807

Rev. High Pressure Sci. Technol. 2-2,171-173(1993)
Gasket:the base of diamond anvil technique
Takehiko YAGI
Selection and machining of a gasket is the base of diamond anvil technique. Mechanical property of the gasket material primarily affects to the thickness of the sample chamber. The way of selection and the machining of the gasket, as well as the compression technique of diamond anvil, are described.
東京大学物性研究所 Institute for Solid State Physics, University of Tokyo
〒277-8581 柏市柏の葉 5-1-5 5-1-5, Kashiwanoha, Kashiwa-shi, 277-8581

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