In memory of the late Professor Tadashi Makita, the first president and the permanent advisor of the Japan Society of High Pressure Science and Technology, this article reviews his personal history, major scientific achievement and his personality including philosophy as a scientist. Dr. Makita was born in Osaka on August 23, 1925. He received a Bachelor of Science degree in Chemistry in 1948, and a Doctor of Science in Physical Chemistry in 1960 from Kyoto University. After filling various posts at Kyoto Institute of Technology from 1949 to 1966, Dr. Makita moved to Kobe University in1967, where he was a professor of high-pressure physical chemistry in Department of Chemical Engineering, Faculty of Engineering during 22 years. His main works were concerned in the effect of temperature and pressure on the thermophysical and physico-chemical properties of fluids. Dr. Makita received the second Y. S. Touloukian Award at the Eleventh Symposium on Thermophysical Properties in Boulder, Colorado, U. S. A. on June 24, 1991 for his distinguished achievement in the thermophsical property research of fluids under high pressure. He regretfully succumbed to cancer on April 9, 1994 aged 68 years.
In memory of the late Professor Tadashi Makita, the present article reviews some of the major scientific achievement he has achieved throughout his distinguished career in thermophysics over the last 40 years. Specific emphasis is given to three major contributions that Professor Makita has devoted himself at the High Pressure Data Center of Japan, Japanese Association of Refrigeration and the Japanese National Committee on the Properties of Water and Steam. The present author has also been involved in these three different activities in collaboration with Professor Makita with whom the present author being acquainted for more than 25 years. Some of the living lessons that the present author has learnt from him in different occasions of revealing the thermophysical properties of fluids of technical importance are also described.
Volumetric measurements as functions of temperature and pressure are necessary not only to describe thenmodynamically the state of a pure liquid or a mixture, but also to evaluate the PVT properties and the effect of pressure on the thermodynamic properties. The compression k, i. e. the relative volume decrease at constant temperature, has been measured by means of two types of piezometer methods for a variety of organic liquids and their aqueous mixtures at different conditions of pressure or composition . In this review, we summarize the results of k measurements for them and give some comments on the related properties determined from the k data after comparing among the systems. The composition dependence of compression and isothermal compressibility for the mixtures is explained in terms of the partial properties of the components.
Ultrasonic speed in fluids is one of the most important physical properties, which is closely related to the thermodynamic quantities. This article reviews the experimental technique for measuring the ultrasonic speed μ, its behavior in liquids at high pressures, and the estimation of the liquid density from the μ data. The temperature and pressure dependencies of the ultrasonic speed in halogenated benzenes are discussed. As a new attempt of the density estimation from the μ data, the liquid molar volume for these substances has been derived by means of the Peng-Robinson equation of state with a reasonable accuracy.
The application techniques of fluid mixtures are recently developed for improving the thermodynamic performance of Rankine cycles. In the power plants, for instance, the better thermal efficiency can be attained with the aid of the Kalina cycle if water is replaced by a mixture of ammonia and water. In case of the refrigerators and heat pumps, the Lorenz cycle is suggested with the use of mixtures of refrigerants for obtaining the better coefficient of performance. In this point of view, the behaviors of vapor liquid equilibria are discussed in conjunction with the Kalina cycle and the Lorenz cycle.
Surface tension measurements of fluids under high pressure is described here. A topic focused on is the fluorocarbon refrigerants and altemative refrigerants, since the authors have much experience for these fluids. The principle and the experimental apparatus of capillary rise method is briefly explained, since this method is widely utilized to measure the surface tension under high pressure. This article introduces the summary of the experimental results and correlation for surface tension of HCFCs and HFCs which are the candidate fluids for alternative refrigerants.
The refractive index is an important optical property, and it is closely related to density by the Lorentz-Lorenz equation. The present status of the measurements of the refractive index coexistence curve is described with a special attention to alternative refrigerants recently studied. The values of critical refractive index of refrigerants estimated in the various references are tabulated. In case of HFC-32, the density coexistence curve in the critical region calculated from refractive index data is compared with that directly obtained from PVT measurements.
The viscosity of gases is greatly altered with increasing pressure and density. The pressure effects on the viscosity of gases are summarized from both experimental and theoretical points of view. The theories, the generalized correlation methods, and the empirical formulations are reviewed. Interesting phenomena such as the negative initial pressure dependence of the gaseous viscosity and the critical anomaly are also discussed.
Pressure (0. 1-400 MPa), temperature (283. 2-323. 2 K), and concentration (0-3 mol kg-1) dependences of the viscosity of aqueous NaCl, R4NBr, NH4Br, and CsCl solutions are surveyed. The pressure dependences of the activation energies, Ev, for the viscous flow and the Jones-Dole's B coefficients are shown graphically for several aqueous electrolyte solutions. A physico-chemical interpretation is given to the behavior of Ev and B with pressure from the view point of the water structure.
In response to the earnest requirement in both science and industrial technology, several new devices for measurements of thermophysical properties have been developed. This article reviews briefly the experimental techniques for measurement of the viscosity and the thermal conductivity of fluids. A special topic focused on is the applicability of the transient hot-wire method to the measurement in dilute gas region. Some technical problems are discussed refering to the authors' experimental data as well as the recent theoretical discussions in the literature.
The hydrothermal hot-pressing technique is one of the solidification methods for inorganic powders by hydrothermal treatment at low temperatures below 350°C with mechanical compression of the powders. This article shows the principle and the apparatus for hydrothermal hot-pressing technique and presents the properties of some solidified materials prepared by this technique.
Supramolecular chemistry is the study of the structure and functions of the supramolecules that result from binding substrates to molecular receptors [1a]. In this field, many chemists have been challenging either to reproduce highly sophisticated reactions occuring in living bodies, or to construct intelligent molecular systems with refined functions. This review describes representative examples of applications of high pressure to supramolecular chemistry, including the results of our efforts to construct certain supramolecules at high pressures.
Cs2Au2X6 (X=Cl, Br, I) are mixed valence complexes with Perovskite-type structure. Recently, we have elucidated the structural P-T phase diagram of these complexes under high pressures and high temperatures for the first time. When the pressure is applied at room temperature, Cs2Au2X6 (X=Cl, Br, I) undergo a tetragonal-to-tetragonal phase transition at 11 GPa, 9 GPa and 5. 5 GPa, respectively. This transition is regarded as a band Jahn-Teller transition driven by the AuI, III→AuII transition. The cubic perovskite structure appears under high pressures and high temperatures for all the three complexes. The cubic phase is obtained as a metastable state at room temperature and ambient pressure. The Au valence states in the second tetragonal phase and the cubic phase are considered to be AuII.
Diamond anvil cell is a high pressure device enough compact to be easily assembled on the powerful 3He/4He dilution refrigerator . Recent developments on electric and magnetic measurements under extreme conditions of high pressure and low temperature are reported.