Education in elementary and junior high schools is reviewed and discussed in relation with heat and energy. There are many subjects concerning heat and energy, especially in elementary schools. They are estimated to amount to about 46 % of the total content of science. Many experiments, while feasible only with simple apparatuses and by pupils themselves, help them to construct diverse concepts about things. It is important to make them have such experiences at their early stage in the schools. There are many educational materials as well which are potentially to be changed in future, and supports are needed to the education in schools.
Lab. of Natural Science Education, Faculty of Education, Fukui
Univ.
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By reviewing the current curriculum of high school science, the status of heat and energy education was analyzed. In spite of the importance of heat and energy education for fostering scientific literacy required in daily life, the comprehensive education on heat and energy is weakened by an optional system of science subjects at high schools. For promoting education on "Science and Technology for the Environment and Society (STES)", it is required to develop teaching materials and educational programs on energy-environment education in addition to the introduction of a compulsory science subject for the first year class at high school.
Graduate School of Education, Hiroshima Univ.
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Oral tests have been effectively introduced in the lessons of undergraduate experimental physics at Gunma University. We show questions and answers actually exchanged with students concerning the basic concepts of thermodynamics, and show student's weak point in their understanding of energy and entropy. Considering the actual ability of students, we have improved our lecture courses by introducing demonstration experiments. Those demonstrations are powerful for students to acquire right concept of thermodynamics, when suitable explanations concerning the history of thermodynamics are given at the same time.。。Finally, we emphasize the importance of viewpoint based on the thermodynamic concepts in future university education.
Professor Emeritus, Gunma Univ.
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Thermodynamics is taught in universities and colleges as a part of physical chemistry or general chemistry. It is a basic discipline and is required in later studies when the students specialize in various fields of science and engineering. There are different organizations of thermodynamics courses with respect to how the entropy is introduced: the traditional Carnot-Clausius-Kelvin-Planck approach, the axiomatic Caratheodory approach, the formal approach by Callen, and Boltzmann's statistical definition of entropy and Gibb's statistical mechanics. The author finds the combination of the traditional approach and elementary statistical method the most accessible for students in introductory thermodynamics courses. Based on the belief that the lack of thermal events in our daily experience in which the entropy is conserved lies at the core of the difficulty we have when we try to understand the entropy concept, the author has contrived an experiment for demonstration in thermodynamics courses in which the temperature of an elastic rubber band is measured as it heats and cools in response to elongation and contraction. Reversibility of the temperature change demonstrates the existence of a conserved quantity, other than the energy, in this thermal event. Connection of this experiment with the Carnot cycle and the Boltzmann entropy is made complete by the knowledge of the random structure of rubber polymers.
(Formerly) Graduate School of Science, Osaka Univ.
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The Significance of education on calorimetry and thermal analysis for undergraduate students was discussed, and the necessity of developments of teaching materials for laboratory classes was pointed out. As the examples of such teaching materials, (1) Thermal Analysis of Phase Behavior of KNO3, (2) DSC of PET (poly(ethylene terephtalete)), and (3) Thermal Decomposition of Basic Copper(II) Sulfate were introduced in a format of reference material for students at universities.
Graduate School of Education, Hiroshima Univ
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To explain the roles of thermodynamics and the measurements of
thermal properties in a Japanese chemical company, four brief reviews
related to thermal behaviors and the evaluations for them were shown.
Thermodynamics and thermal characterization will be able to play
important roles in many companies, though it is not yet well
recognized because many researchers have not sufficient knowledge
about thermal behaviors of materials.
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Activity of tin in liquid Sn-Bi-Sb was derived by EMF measurement of galvanic cell with fused salts electrolyte in the temperature range of 700 to 1000 K in the whole composition range. Activity of tin at 900 K shows very small positive deviation from Raoult's law for Sn-Bi alloys and moderately negative deviation for Sn-Sb alloys. Activity of ternary alloys along・マ SbyBi(1。ンy)-Sn (y。�0.25, 0.50 and 0.75) shows negative deviation and the deviation becomes large with increasing Sb content. Excess free energy of mixing is derived using Darken's method for Gibbs-Duhem equation and the values are compared with those by model calculations based on the three constitutive binary data.
Graduate School of Eng., Osaka Univ.
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It is described that genomic-DNA sequence analyses of many living organisms have been completed, and studies on structural and functional genomics are now proceeding. The dual nature of natural proteins is remarked that they have two different aspects of technological and scientific entities, which is distinct from industrial functional elements. Characteristic aspects of the molecular thermodynamic quantities of proteins, and their physical and biological implications are explained including the enthalpy-entropy compensation and the large positive heat-capacity change in protein denaturation. Finally, perspectives on the research of protein thermodynamics at the post-genome era are presented and a possibility of the development of protein science in the expanded sequence space is discussed.
Dept. of Bioengineering, Nagaoka Univ. of Technology
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A differential AC chip calorimeter based on commercially available sensors is described. Due to the differential setup pJK。ン1 sensitivity is achieved. Heat capacity can be measured for sample masses below one nanogram. This corresponds to heat capacities below one nJK。ン1 even above room temperature as needed for the study of the glass transition in nanometer thin polymeric films. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the broad frequency range from 1 Hz to 1 kHz for sample masses of some nanograms.
Institute of Physics, University of Rostock
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A high sensitivity and high resolution DSC working between 220 and 400 K with a baseline stability of 。゛3 nW, with a low noise of nV order, with a quick response time of 2 s and with a temperature resolution of 0.1 mK, capable of measuring in the both directions of heating and cooling has been designed and constructed. The stability of the baseline was achieved by the use of a high sensitive temperature sensor, a precise temperature control of 。゛0.1 mK, an adiabatic control, the damping devices to decrease the temperature fluctuation at the sample cell and the devices to decrease noises on the lead wires. Very fine structures of phase transitions were observed at a cooling rate of 5 mKs。ン1 in the measurement of C22H46 by application of the nW-stabilized DSC. The measurement of the melting of C15H31COOH and C32H66 employing very small samples of mg order was carried out as well and the results demonstrated the high sensibility of the nW-stabilized DSC.
Faculty of Education, Chiba Univ.
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Movement is a fundamental characteristic of all living things. This biogenic function is attributed to molecular motors in a cell. Molecular motors are mechano-chemical enzymes that generate forces by using chemical energy derived from the hydrolysis reaction of adenosine tri-phosphate (ATP) molecules. Despite a large number of studies on this issue, the mechanism of mechano-chemical energy transduction is still unsolved. In this review, we describe the experimental and theoretical approaches for elucidating the mechanism how kinesin motors generate the unidirectional movement along a microtubule. By use of a novel single-molecule-detection technique, we detected the elementary processes on the sliding movement of single kinesin molecules. Motility analysis has revealed that a stochastic mechanism underlies in the unidirectional movement of kinesin. To explain the energetic aspects of the stochastic movements, we constructed a new phenomenological framework based on non-equilibrium statistical mechanics, and determined the energetic balance in single kinesin molecules. It is indicated that the hydrolysis energy of ATP is effectively used to generate the unidirectional movement. Our experimental and theoretical approaches will help to understand thermodynamics of nano-world.
Graduate School of Science, Kyoto Univ.
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Binary phase diagrams of nano-particle alloy systems have been evaluated from the information on the Gibbs energy and the surface tension of bulk systems. As the size of a particle decreases, the melting point of pure component decreases and the liquid phase region is enlarged in binary phase diagrams, in other words, the liquidus temperature decreases. In addition, solid solutions in nano-particle systems have larger composition ranges than those in bulk alloys. It is found from the above evaluation that the size dependence of a particle on phase diagrams is remarkable when excess Gibbs energies have large positive values in solid and liquid phases.
Graduate School of Engineering, Osaka Univ.
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The heat radiation, from the Sun at 6000 K to space at 3 K, gives rise to the meteorological and biological activities on the Earth. Therefore, irreversible processes, expressed by the second law of thermodynamics, originate in the expansion of the universe, which keeps space at 3 K. Thermodynamics as formulated by Clausius is primarily a theory, not of energy, but of matter, and "entropy" is a quantity of state expressing "transformational content" of a body. The entropy increase produced by the irreversible processes of heat transfer and diffusion is derived thermodynamically, and Boltzmann's principle deduced. Gibbs's paradox derived from the entropy of mixing, and light-quantum theory from the entropy of radiation, show that thermodynamics contained the germ of quantum theory. Non-equilibrium thermodynamics based on the local equilibrium assumption, and the theory of dissipative structure, explain behavior of matters and formation of structures we meet everyday. Finally, it is argued that the application of the concept of entropy to economic processes highlights the importance of the problems of resource and environment.
Seirei Christopher College
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Gibbs energy is the most important thermodynamic quantity for the discussion of equilibria in chemistry. This paper is for persons who have not opened textbooks of thermodynamics after leaving the school. We shall see that the direction of spontaneous change is firstly obtained in terms of the Gibbs energy of substances, and secondly the maximum non-expansion work obtained from a process at constant temperature and pressure is given by the Gibbs energy change of the process. We shall make another description such as, the properties of Gibbs energy, phase diagram of a substance, colligative properties of solutions, and reaction Gibbs energy in chemical reaction. Finally, we shall deal with the determination procedure of Gibbs energy and discussions of the obtained results in binary solutions as an application to the real system.
Frontier R&D Center, Tokyo Denki Univ.
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The basic relationship between binary phase diagrams and the thermal analysis charts is described. The phase diagram of Al-Mg system is determined based on the DSC charts. An interesting mystery is given on the freezing behavior of water-ethyl alcohol system; The DSC charts cannot be interpreted based on the simple phase diagram.
Agne Gijutsu Center
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Through thermodynamic analyses and considerations on the existing experimental results on cubic mesophases, the unexpected sharing of the common properties by thermotropic and lyotropic liquid crystals is demonstrated. In some thermotropic liquid crystals, the terminal alkyl chain attached to the molecular core is highly disordered as indicated by the magnitude of configurational entropy. The melt chain serves as intramolecular solvent (self-solvent), as evidenced by the close similarity between phase diagrams against chain-length and composition in binary system with n-alkane. These facts lead to the quasi-binary (QB) picture of thermotropic liquid crystals. The QB picture affords the basis to establish the structural models of cubic mesophases in classic cubic mesogens, and that to deduce the entropy difference between flat surfaces and complex surface(s) having complicated geometry such as Gyroid, a triply periodic minimal surface (TPMS).
Graduate School of Pure and Applied Sciences, University of
Tsukuba
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In high-pressure high-temperature conditions in the earth's interior, constituent minerals of the mantle transform to denser phases. The most abundant mineral, (Mg, Fe)2SiO4 olivine, transforms to high-pressure phases with spinel structure and (Mg, Fe)SiO3 perovskite plus rocksalt-structured (Mg, Fe)O at the depths where seismic velocities suddenly increase. The equilibrium transition boundaries for the high-pressure transitions of olivine have been accurately determined by high-pressure high-temperature experiments and thermodynamic calculation based on calorimetric data. The results have been used to estimate temperature distribution in the mantle. High-pressure phase relations of pyroxenes and garnet have also been determined by high-pressure experiments and thermodynamic calculation. Combining the phase relations of the mantle minerals, constitution of the deep earth has been mostly clarified. Recent progress in high-pressure experiments has strongly suggested that Mg-rich perovskite further transforms to a denser structure near the base of the mantle.
Dept. of Chemistry, Gakushuin Univ.
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Recently, we succeeded in vitro time-resolved x-ray observations of picometer-scale slow Brownian motions of individual protein molecules in aqueous solutions. In this new single molecular detection system, which we call Diffracted X-ray Tracking (DXT), we observed the rotating motions of an individual nanocrystal, which is linked to the specific site in individual protein molecules. Therefore, DXT can monitor dynamics of the individual molecules or specific sites in individual single protein molecules. Now, we observed individual DNA molecules, myosin head molecules, denatured proteins, protein membranes.
SPring-8/JASRI & JST/ CREST (Sasaki-Team)
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In this article is dealt with the history of the concept and the
measuring method of temperature. Firstly, the relation of thermal
sensation of human body to the temperature concept is discussed.
Secondly, the rise and development of liquid-in-glass thermometers
are described. Thirdly, the formation of thermodynamic concept of
temperature is traced. Finally, the modern trends of
conceptualization of temperature both in operationism and
reductionism are pointed out.
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This review describes the analytical techniques for evaluating the structural phase transition of a small protein. First, it outlines the significance of thermal analyses in protein research. Next, a practical limitation of micro DSC to detect the structural phase transition of a small protein is mentioned, though this method is adequate for ordinary proteins. We then introduce the strategy for analyzing a small protein combining the optical measurements using chemometrics and the atomic level analyses by NMR, which were conducted by us to overcome the above problem. Finally, the meaning of the thermodynamic result obtained from these analyses is discussed.
National Institute of Advanced Industrial Science and
Technology
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General theoretical scheme for・マ studying phase diagrams of associating polymer solutions is presented. As the simplest example, phase diagrams with lower critical solution temperature (LCST), as seen in aqueous solutions of neutral polymers such as poly(ethylene oxide) and poly(N-isopropylacrylamide), are theoretically derived and compared with the recent experiments. It turns out that miscibility gaps of loop shape and hourglass shape appear depending upon the polymer molecular weight if hydration (association of water molecules onto the polymer chains by hydrogen bonds) takes place randomly and independently, while miscibility gaps of square shape with very flat LCST line appear independently of the polymer molecular weight if hydration is cooperative.
Dept. of Polymer Chemistry, Graduate School of Engineering, Kyoto
Univ.
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Factors affecting the ionic conductivity of lithium have been discussed in this paper. Firstly, limitations of the classical concept were shown, such as Born-Mayer equation for the prediction of the activation energy during ionic migration. These classical concepts roughly reproduce the experimental behavior, however the deviations from the prediction occasionally occur. Some of the reasons for such deviations are due to the assumptions that the crystal was composed of perfect ionic bonds, no local structural distortion around defect site, and defects are not interact one another. To understand these effects, recent experimental and computational works are reviewed.
Dept. of Applied Chemistry, Tokyo Institute of Technology
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Extensive usage of fossil fuels is causing CO2 emission increase
and rapidly increasing the atmospheric CO2 concentration which causes
the global warming. The atmospheric CO2 concentration should be
stabilized at a low level to mitigate the global warming.
Herein, projections of the world population, economic growth, energy
consumption and energy sources in 100 years, which affect the CO2
emissions, are explained. CO2 mitigation measures, especially, carbon
capture and storage technologies which are considered to be
necessarily implemented for a world based on fossil fuels are
described.
Research Institute of Innovative Technology for the Earth
Scanning tunneling microscopes (STM) that can operate under UHV at low temperatures have been developed. STM observations of Bi-based oxide superconductors have shown that Pb atoms occupying Bi sites and Sr-site defects could be imaged selectively by appropriately setting bias voltage. Furthermore, scanning tunneling spectroscopic measurements have successfully visualized electronic phase separation into superconducting and non-superconducting domains. A variable temperature SPM instrument with sub-micron scale resolution and wide scanning range up to 15 mm has also been constructed. The instrument enables us to measure local magnetic and electric properties by using a miniature SQUID sensor and cylindrical resonator tube, respectively, as scanning probes. The former was applied to direct observation of vortices trapped in La1。ンxSrxCuO4. The latter was utilized to investigate conductivity of a Mn-based oxide, Nd1。ンxSrxMnO3, as functions of chemical composition x and temperature, in a systematic manner.
Tokyo Univ.
The data of heat capacity, thermal conductivity, and thermal expansion behavior for materials in solid oxide fuel cells (SOFCs) are reviewed. Most of the SOFC materials are complex metal oxides and their thermal conductivities are generally low, that causes a large temperature distribution during the operation. Since the SOFC consists of metal oxides and composites, a good thermal expansion matching is the most important point in order to fabricate durable cells and stacks. The electrolytes and interconnects are exposed in a large gradient of oxygen partial pressure at a high temperature, and isothermal expansion is observed for rare earth substituted ceria and alkaline earth substituted lanthanum chromites. Although the isothermal expansion in lanthanum chromites can be alleviated by substituting the transition metals, it can not in rare earth substituted ceria.
AIST
Almost all the numerous forms of ice including 13 crystalline phases, several distinct amorphous states as well as clathrate hydrates have been characterized in terms of their thermal conductivity k. A few deviations from both the typically strongly decreasing k(T) (k。チT。ン1) associated with crystals and the weakly increasing k(T) associated with glassy states are observed. In particular, the crystalline clathrate hydrates show glass-like k, whereas low-density amorphous (LDA) ice shows crystal-like k (k。チT。ン0.6). The latter is unique for an amorphous state and indicates that LDA ice exhibits a surprisingly high degree of structural order that allows for high-frequency phonon propagation. It also implies that LDA ice is not the glassy counterpart of ambient liquid water that shows typical amorphous-like behavior. Moreover, the crystalline ices Ih and Ic and LDA ice exhibit abnormal negative pressure coefficients of k. Both ices Ih and Ic demonstrate pressure-induced amorphization to high-density amorphous (HDA) ice, a state to which also LDA ice transforms on pressurization. The negative pressure coefficient is a signature of phonon softening which leads to a disordering transition upon pressurization.
Department of Physics, Ume� Univ.
Phase transitions and critical phenomena have been central subjects in condensed-matter physics, where calorimetric investigations play a significant role. In this review, we focus on the study of critical heat anomaly in liquid crystalline phase transitions. Liquid crystals exhibit amazingly wide variety of phases, and therefore provide attractive examples for studying the phase transitons and critical phenomena. First, some of the basic liquid crystalline phases are described, and then elementary ideas of critical phenomena and universality are briefly reviewed. Developments in high-precision calorimetric techniques have greatly contributed to the investigations of critical phenomena in liquid crystal systems. In this review, analyses of critical heat anomalies have been described in detail: necessity of including critical constant term, correction terms, and also data-range shrinking, etc. Finally, examples of recent investigations are shown. The critical heat anomaly observed in antiferroelectric liquid crystals exhibits crossover from 3D XY to tricritical behavior. The results on the de Vries Sm-A。ンSm-C phase transition are also displayed.
Tokyo Institute of Technology
Theory of associating polymer solutions introduced in Part I is applied to thermoreversible gelation induced by pairwise cross-links of polymers. Phase diagrams showing coexisting phase separation and gelation are derived. The theory is then extended to gelation with multiple cross-links to study aqueous solutions of associating polymers whose network junctions are formed by micelles of hydrophobic groups. The effect of hydration leading to phase diagrams with LCST coexisting with low-temperature gelation is studied and compared with the recent experiments.
Kyoto Univ.
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