熱測定 NetsuSokutei 31 (1), 2-5 (2004)
【 論 文 】
ブルース石の脱水を用いた超高圧下における定量的示差熱分析の試み
福井宏之，桂 智男，大高 理
Quantitative Differential Thermal Analysis of Dehydration of Brucite under
High Pressure
Hiroshi Fukui, Tomoo Katsura, and Osamu Ohtaka
Dehydration of brucite was measured by means of high-pressure differential
thermal analysis (HP-DTA). The enthalpy of the dehydration was derived
as a function of temperature and pressure from thermodynamic quantities
of brucite, periclase, and H2O fluid. The dehydration of brucite is likely
to be used to quantify an HP-DTA system up to 6 GPa. The system calibration
factor was determined to be 1.2×10－3 J K－1 s－1.
ブルース石の脱水反応を高圧示差熱分析（HP-DTA）により測定した。ブルース石，ペリクレイス及びH2O流体の熱力学データから，ブルース石の脱水反応熱を温度と圧力の関数として算出した。ブルース石の脱水反応熱は6万気圧まで，高圧下での定量的示差熱測定の熱量の基準として使用できると考えられる。装置定数は1.2×10－3
JK－1 s－1となった。
大阪大学
Osaka University
熱測定 NetsuSokutei 31 (1), 6-13 (2004)
【 小 特集－水 解 説 】
水の多様性；ダイナミックスと反応性
斉藤真司，松本正和，大峰 巖
Water; Dynamics and Reactions
Shinji Saito, Masakazu Matsumoto, and Iwao Ohmine
Various aspects of Water Dynamics are discussed;
(1) Fluctuation and relaxation in hydrogen bond network rearrangement and
their observation, (2) Mechanism of water freezing, and (3) Proton transfer
in liquid water and ice. Liquid water yields the intermittently collective
motions accompanied with large fluctuations. Various relaxation
processes associated with these collective motions in liquid water yield
so-called 1/f spectra. We present the result of our analysis on a method,
called 2-dimensional Raman/IR spectroscopy. This method will be able to
deal with the mechanism of these intermittent collective motions.
Upon cooling, water freezes into ice. This process is a most familiar phase-transition,
occurring in many places in nature, but has never been successfully simulated
by a computer simulation. We report the first successful simulation for
the pure water freezing process, which gives a molecular level picture
of, particularly, how an initial nucleus is created and grows.
The proton transfer is a most basic reaction in chemistry and biochemistry.
It is found that the mechanism of the proton transport in ice is completely
different from that in liquid water. The repulsion from fourth coordinated
water makes the facile proton transfer possible. The long range solvation
is essential for the smooth transport of the proton in ice.
最も一般的な液体であり多くの物理科学的な多様性を示す。その多様性の発現機構の源である水素結合のネットワークの構造変化とそれが引き起す化学反応の機構を探る。そのような「水の多様な特性の発現機構」に関係する次の三つの課題；①
水の中の水素結合ネットワークの構造変化の特性，特にその長時間変化の様相と，またネットワーク構造変化伴う水の中の集団運動・揺らぎを観測するための新しい実験法について，②
水の氷化の分子論的機構（水は如何にして結晶に凍るのか？）について，また③
水や氷中のプロトン移動の機構について，の最近の研究について述べる。
名古屋大学
Nagoya University
熱測定 NetsuSokutei 31 (1), 14-22 (2004)
【 小 特集－水 解 説 】
超臨界水の構造と物性
中原 勝
The Structure and Properties of Supercritical Water
Masaru Nakahara
First we explain the importance of the investigation
on the structure and properties of supercritical water in relation to the
chemical evolution and the environmental and energy issues of the 21st
century. Molecular interpretations are given to the temperature dependence
of the density, dielectric constant, and viscosity, hydrogen-bonding structure,
and dynamics of supercritical water. The three-dimensional network structure,
characteristic of ambient water, is broken down in hot expanded water at
temperatures higher than ～200℃ and densities lower than ～0.9 g cm－3.
The number of hydrogen bonds per molecule has been determined by the NMR
method combined with computer simulation; it decreases from ～4 for ambient
water to 1-2 for supercritical water at 400℃ and the critical density
(～0.32 g cm－3). The NMR rotational correlation time (t2R) for supercritical
water at the medium densities is in the range of 50-70 fs, two orders of
magnitude smaller than the ambient value (2 ps). Supercritical water is
shown to be an alternative to hazardous organic solvents; there are being
found new hydrothermal organic reactions without catalyst for the development
of green chemistry.
化学進化・地球環境・エネルギー問題の観点から，新しい学術創生のために超臨界水および超臨界水溶液の物性・構造・ダイナミクス・反応の研究が必要であることを強調した。相互作用の本質である水素結合が水の物性と構造を支配することに着目して，解説した事項は次のもの。臨界点と分子間相互作用の関係，圧力と密度と温度の関係，誘電率と温度の関係，粘性係数と温度の関係，水素結合構造，回転相関時間と温度の関係，超臨界水反応の熱化学。可能な限り，観測量の分子論的な解釈を試み，今後の展望を示した。
京都大学
Kyoto University
熱測定 NetsuSokutei 31 (1), 23-29(2004)
【 小 特集－水 解 説 】
水のポリアモルフィズムと第二臨界点仮説
三島 修
Polyamorphism in Water and the Second Critical Point
Hypothesis
Osamu Mishima
Liquid water shows the eccentric properties at low
temperatures such as the maximum density at 4℃. The amorphous solid form
of water also shows a peculiar phenomenon known as polyamorphism. Poole
et al. has proposed the second-critical-point hypothesis of water and explained
these properties. The experimental and theoretical studies support the
hypothesis, but further proofs are required.
水は4℃密度極大など低温で奇妙な性質を示す。アモルファス氷もポリアモルフィズムとして知られる特異な現象を示す。Poole等は水の第二臨界点仮説を提唱してこれらを説明した。その仮説は実験や理論研究で支持されているが，更なる証明が要求されている。
物質・材料研究機構
NIMS
熱測定 NetsuSokutei 31 (1), 29-36 (2004)
【 解 説 】
マキシマムエントロピー法による電子密度分布
坂田 誠，西堀英治，高田昌樹
Experimental Charge Density Distribution by the Maximum Entropy Method
Makoto Sakata, Eiji Nishibori, and Masaki Takata
The accurate charge density studies by the Maximum Entropy Method (MEM)
utilizing X-ray diffraction is outlined with some examples. The basic concept
of the method is stated in some details. In addition, some experimental
charge densities are given to demonstrate the usefulness of the method,
such as endohedral metallofullerenes, metal hydride and intermetallic compounds.
In La2@C80 metallofullerene case, the extraordinary charge density distribution
is revealed, that is two La atoms form pentagonal dodecahedron charge density
due to the hopping motion inside fullerene cage. In MgH2 metal hydride
case, charge density peaks of hydrogen atoms are clearly found in MEM charge
density map, whereas no such charge density peaks are found in direct Fourier
charge density map.
X線回折を用いたマキシマムエントロピー法による精密電子密度分布解析について，幾つかの例とともに，その概要を説明した。基本的な考え方については，多少，詳しく述べた。この方法の有用性を示すために金属内包フラーレン金属水素化物，金属間化合物の解析例を示した。金属内包フラーレンLa2@C80においては，2個のLa原子が，フラーレン・ケージ中でのホッピング運動により5角形からなる正20面体型になっていると言う大変に変わった電子密度分布が見出された。金属水素化物MgH2においては，直接フーリエ法による電子密度ではまったく見られない水素原子の電子密度ピークがMEM電子密度により発見されているという興味深い結果が得られている。
名古屋大学
Nagoya University
熱測定 Netsu Sokutei 31 (2), 62-68 (2004)
【 論 文 】
Excess Enthalpies of Some Nitrile Compounds ＋ Methyl Methylthiomethyl
Sulfoxide or ＋ Dimethyl Sulfoxide at 298.15 K
Takayoshi Kimura, Takanori Matsushita, Kenzi Suzuki, and Sadao Takagi
Excess enthalpies of binary mixtures between each of acetonitrile, propionitrile,
butyronitrile, pentanenitrile and benzonitrile＋methyl methylthiomethyl
sulfoxide (MMTSO) and＋dimethyl sulfoxide (DMSO) have been determined at
298.15 K. All mixtures showed positive enthalpy change over the whole range
of mole fractions except acetonitrile + DMSO over 0.95 in mole fraction
of DMSO.
Partial molar enthalpies of the mixtures of acetonitrile(1)＋DMSO (2)
around 0.65 in mole fraction have maximum of HE1 and minimum of HE2. Linear
relations are obtained between limiting excess partial molar enthalpies
and (m12 m22)(r1＋r2)－6 except the mixtures containing for benzonitrile.
However limiting excess partial molar enthalpies of the mixtures of aromoatic
compounds＋MMTSO or＋DMSO showed good relation with (a2m12＋a1m22)(r1＋r2)－6.
アセトニトリル，プロピオニトリル，ブチロニトリル，ペンタンニトリルおよびベンゾニトリル＋メチルメチルチオメチルスルホキシド（MMTSO）あるいはジメチルスルホキシド（DMSO）との混合エンタルピーを298.15
Kで測定した。測定した混合エンタルピーはアセトニトリル＋DMSO系の0.95以上の濃度を除いてすべて吸熱系であった。
アセトニトリル＋DMSO系のモル分率0.65付近に部分モルエンタルピーH1Eの極大とH2Eの極小が見出された。ベンゾニトリル系を除いて(m12m22)(r1＋r2)－6と部分モルエンタルピーはよい相関を示した。また芳香族化合物系の部分モルエンタルピーは(a2m12＋a1m22)(r1＋r2)－6とよい相関を示した。
近畿大学, Kinki University
熱測定 Netsu Sokutei 31 (2), 69-73 (2004)
【 小特集－医薬品の安定性評価と熱測定 解 説 】
医薬品分子状態のDSC測定による評価
戸塚裕一，山本恵司
Evaluation of Molecular State of Medicines by Differential Scanning Calorimetry
Yuichi Tozuka and Keiji Yamamoto
This review describes the evaluation of molecular state of medicines by
using differential scanning calorimetry (DSC). Thermal behavior of amorphous
clarithromycin obtained by grinding and spray drying were evaluated. In
DSC curves, both broad and sharp peaks for crystallization were observed
in 30 min ground sample, whereas spray-dried sample showed one broad peak
for crystallization. In order to study the physicochemical stability of
amorphous cefditoren pivoxil, glass transition accompanying enthalpy relaxation
was evaluated for the ground and spray-dried samples by means of modulated-temperature
DSC. Glass transition temperature (Tg) and relaxation enthalpy of the ground
sample of cefditoren pivoxil were changed by storage for definite intervals
at a temperature below Tg, while those of the spray-dried sample indicated
an almost constant value by storage. These results suggest that the ground
sample was less stable than the spray dried sample. The ground sample might
be stabilized by storage below Tg. Thermal behavior of salicylamide in
the mixtures with Folded Sheets Mesoporous Materials (FSM)-16 was investigated
by DSC. Three kinds of molecular states of salicylamide, i.e., crystalline
state, disordered crystalline state for which a broad endothermic peak
was observed at a lower temperature, and amorphous state for which no peak
on the DSC curves could be observed.
DSCを用いて医薬品の分子状態の評価を行った。粉砕および噴霧乾燥処理により得られた非晶質ClarithromicinのDSC測定を行ったところ，結晶化に伴う発熱ピークの形状が異なっており，30分粉砕物はブロードおよびシャープな二つのピークが認められるが，噴霧乾燥物ではブロードなピークのみが観察された。Cefditoren
pivoxil非晶質の安定性について検討するため，ガラス転移およびエンタルピー緩和に関して温度変調DSCを用いた測定を行った。Cefditoren
pivoxilの噴霧乾燥物および30分粉砕物をそれぞれガラス転移温度以下で等温保存した時，噴霧乾燥物では保持時間や保存温度を変化させても，Tgおよびエンタルピー緩和量はほとんど変化しなかったが，30分粉砕物では，保存温度と保持時間を変化させることによりTgおよびエンタルピー緩和量は変動した。噴霧乾燥物の安定性は30分粉砕物に比べ高いことが認められており，30分粉砕物は等温保存中に安定化したと推察された。メソポーラスシリカFSM-16(Do)とSalicylamideを混合したときの熱挙動を検討した。DSC測定によりSalicylamideの三つの状態，すなわち，Salicylamide結晶，融点よりも低温側にブロードな吸熱ピークを示す結晶格子に乱れを生じた状態，DSC曲線上で熱の出入りが検知されない非晶質もしくは表面に吸着した状態を区別することが可能であった。
千葉大学, Chiba University
熱測定 Netsu Sokutei 31 (2), 74-79 (2004)
【 小特集－医薬品の安定性評価と熱測定 解 説 】
等温カロリメータによる非晶質製剤の構造緩和の評価
川上亘作
Investigation of the structural Relaxation Process of Amorphous Formulation
by Isothermal Microcalorimetry
Kohsaku Kawakami
The use of isothermal microcalorimetry for analyzing structural relaxation
and recovery processes of amorphous materials is discussed. Unlike the
conventional DSC method, this new method enables to directly monitor the
relaxation process. Also featured in this article is its application for
investigating the recovery process, which has hardly been reported in literature.
The both processes were elucidated using Kohlrausch-Williams-Watts derivative,
although its application for the recovery process needs discussion. The
relaxation parameters obtained by this procedure agreed very well with
those from the DSC method. The advantages and disadvantages of this method
are summarized.
等温カロリメータを用いて非晶質材料の構造緩和および回復過程の評価を試みた。これまで汎用されてきたDSC法と異なり，本手法は緩和過程を直接観察することが可能である。また，ほとんど報告例のない回復過程も評価できることが分かった。両過程ともKWW式の導関数によって解析が可能であり，求められた緩和パラメータは，DSCより求められたものと一致することが確認された。本手法の長所と短所についても考察を行う。
塩野義製薬株式会社, Shionogi & Co., Ltd.
熱測定 Netsu Sokutei 31 (2), 80-86 (2004)
【 小特集－医薬品の安定性評価と熱測定 解 説 】
固体医薬品の安定性評価と微少熱量計の応用
吉橋泰生，米持悦生，寺田勝英
Application of Isothermal Microcalorimetry for
Stability Evaluation of Solid Dosage Form
Yasuo Yoshihashi, Yonemochi Etsuo, and Katsuhide Terada
This review demonstrated the possibility of application of isothermal microcalorimetry
(IMC) for stability evaluation of solid dosage form. Various kinetic equations
derived from the different reaction model in the solid state were applied
for the obtained data using isothermal microcalorimeter. Suitable decomposition
rate constant was successfully derived from the most appropriate kinetic
equation evaluated by curve fitting method. Experimental decomposition
rate constant of solid dosage form was determined by the time-consuming
conventional method, which took more than 6 months. The predicted values
were in good agreement with the experimental values. By using this method,
the stability of solid dosage form can be predicted by a simple operation
in a short time. Application of IMC would be useful for the screening test
for the drug stability.
微少熱量計の固形医薬品の安定性評価への応用について解説した。種々の固体状態での反応速度モデルを，微少熱量計により得られる医薬品の測定データに適用した。最適な反応速度式を実験データにあてはめることにより，医薬品の分解速度定数が予測された。6カ月以上を費やし，従来から行われている煩雑な方法により分解速度定数を求めた。予測された分解速度定数と実際に測定した分解速度定数は良好に一致した。微少熱量計を用いた安定性予測の方法は，簡便かつ短期間での測定を可能とし，この方法は簡便な医薬品の安定性スクリーニング法として有用と考えられた。
東邦大学, Toho University
熱測定 Netsu Sokutei 31 (2), 87-92 (2004)
【 解 説 】
凍結高分子ゲル中の氷晶とガラス化した水
村勢則郎
Ice crystals and glassy water in frozen polymer gels
Norio Murase
To understand the mechanism of ice crystallization during rewarming observed
with a frozen crosslinked dextran gel of a certain density of crosslink,
DSC, Raman scattering and X ray diffraction-DSC simultaneous measurements
were conducted. It was found, as a result, that size of ice crystals as
well as freezing behavior depend on the density of crosslink of the gels.
By the study of two-dimensional X ray diffraction-DSC simultaneous measurements,
formation of small ice crystals was indicated with the gel where ice crystallization
during rewarming is observed. Presence of glassy water was also indicated
in the frozen state of the gel by the measurement of Raman scattering.
Then, it was clarified that ice crystallization in polymer gels is more
or less obstructed by the polymer network, and by its change at the time
of freezing. From these results together with the knowledge so far obtained,
a conceivable mechanism of ice crystallization during rewarming was discussed.
凍結した架橋デキストランゲルを昇温すると，架橋密度が適当な場合，氷晶形成による結晶化現象が観測される場合がある。この昇温結晶化のメカニズムを解明する目的で，DSC，ラマン散乱，X線回折－DSC同時測定を行った。その結果，凍結挙動だけでなく，生成する氷晶のサイズも架橋密度に依存することが明らかになった。すなわち，二次元X線回折－DSC同時測定の結果から，昇温結晶化の観察されるゲルではサイズの小さな氷晶の形成されやすいことが示唆された。また，ラマン散乱実験から，このゲルにおいてガラス状態の水の存在が示唆された。したがって，高分子網目構造の存在および凍結時における網目構造の変化により，高分子ゲル中において氷晶形成は妨げられることが明らかになった。これまでに得られた知見より，昇温結晶化のメカニズムについて議論した。
東京電機大学, Tokyo Denki University
熱測定 Netsu Sokutei 31 (3), 100-107
(2004)
【 論 文 】
熱量測定によるZn-Te合金の熱力学的研究
山口勉功
Thermodynamic Investigation of Zn-Te Alloys by Calorimetry
Katsunori Yamaguchi
The heat contents of the ZnTe compound were measured by a drop calorimeter
in the temperature range from 750 to 1600 K. The enthalpy of fusion of
the ZnTe compound was determined as 51.1±0.3 kJ mol－1 at corresponding
melting point of 1573±3 K. The heat content and heat capacity equations
were derived by Shomate function for the solid compound. The enthalpy of
formation of the ZnTe compound and the integral enthalpy of mixing for
the liquid Zn-Te system were measured by direct reaction calorimetry at
800, 1173 and 1373 K using a high temperature twin calorimeter. The enthalpy
of mixing of the liquid Zn-Te phase shows large negative values in the
neighborhood of the compound composition. This behavior dependent anomalies
is explained by a chemical short range order in liquid alloys. The obtained
thermodynamic data for the Zn-Te system was used to reassess the system
following CALPHAD standard. An associated solution model for the liquid
phase and standard Gibbs energy functions for the three solid phases (Zn,
ZnTe and Te) were used. The thermodynamic properties and phase diagram
calculated from the reassessed system agree well with the experimental
data.
熱測定 Netsu Sokutei 31 (3), 108-116
(2004)
【 論 文 】
化学教材の開発における熱分析の意義
－亜鉛塩の沈殿生成反応とその熱分解反応を例として－
田中春彦，松田善信，古賀信吉，古川義宏
The Significance of Thermal Analysis in the Development of Teaching Materials
for Chemistry Education
- As Exemplified by the Precipitation Reactions of Zinc Salts and their
Thermal Decompositions -
Haruhiko Tanaka, Yoshinobu Matsuda, Nobuyoshi Koga, and Yoshihiro Furukawa
Thermoanalytical studies of reactions involving basic zinc salts
were made as an example of application of thermal analysis to the fundamental
research on developing teaching materials for chemistry education. The
studies were complemented by pH titrimetry, thermometric titrimetry, chemical
analysis, IR spectrometry, and X-ray diffractometry. On the basis of the
results, the possibility was suggested that some investigative teaching
materials are developed by introducing the precipitation reactions and
thermal decomposition of the basic zinc salts into chemistry courses at
a secondary education level. It was proposed that the thermoanalytical
measurements for the basic zinc salts applied in the present study are
also utilized successfully as teaching materials for educating thermal
analysis at universities and colleges.
熱測定 Netsu Sokutei 31 (3), 117-124
(2004)
【 講 座 】
微生物のコロニー増殖と熱測定
古賀邦正
Evaluation of the Growth Activity of Microbial Colonies on Solid Medium
using Calorimetry
Kunimasa Koga
In many cases, microbes exist on solid phase. Microbes on solid
phase multiply as colonial growth. It is known that the growth on
solid phase is different from the growth in liquid state. Comparing
with microbes in liquid state, microbes on solid phase are hard to take
nutrients. And the environment of microbes varies from place to place
in the colony and affects the metabolism of microbes.
Information of colonial growth of microbes on solid phase is required
for prevention of putrefaction of solid food, utilization of soil microbes
or investigation of a infection mechanism of pathogenic bacteria to an
organism.
However, the information regarding colonial growth of microbes on solid
phase is not enough compared with that of microbes in liquid state by the
reason of the absence of suitable and quantitative methods of estimating
the colonial growth curve.
In this article, microbial calorimetry is introduced to be the method
suitable for non-destructive measurement of microbial colonial growth on
solid phase. Changes in the metabolic heats of colonial growth with time
(the growth thermogram) are obtained with good reproducibility. The
actual heat evolution curves (f(t) curves) obtained from the thermograms
of growing colonies give good agreement with the changes in viable cell
numbers in colonies under the same conditions. Using microbial calorimetry,
the colonial growth of microbes can be evaluated quantitatively. And still,
the method is useful for evaluation of the complicated phenomenon by microbes
such as putrefaction, and development of novel natural substances which
suppress the colonial growth microbes.
熱測定 Netsu Sokutei 31 (3), 125-132(2004)
【 講 座 】
非定温速度論（1）単一素過程の場合
小澤丈夫
Non-isothermal Kinetics (1) Single Elementary Process
Takeo Ozawa
Fundamental relations are derived for a single elementary process by using
concepts of "generalized time" and "generalized rate". These concepts are
useful for describing reactions in which only a single elementary process
is involved, and by using these useful relations iso-conversion methods
for kinetic analysis, both of integral methods and a derivative method,
are derived and explained with some illustrations. The methods for kinetic
analysis and other descriptions in this article are also applicable to
physical changes of a single elementary process, such as diffusion and
thermal stimulated currents.
熱測定 Netsu Sokutei 31 (3), 133-145(2004)
【解 説】
陽子雲 － 水素原子核の波動性と結晶の物性 －
松尾隆祐
Proton Cloud
- The Wave Nature of Proton and Its Consequences in the Properties of Crystals
-
Takasuke Matsuo
This paper reviews structure and properties of crystals related
to quantum mechanics of nuclear motion. The basic quantum theory of the
harmonic oscillator and free rotor formed by atoms in molecules is briefly
reviewed. It is extended to include tunnel states as explicit indication
of the wave-like property of the nucleus. The term proton cloud is introduced
to describe the delocalized proton. Deuteration-induced phase transitions
in bromohydroxyphenalenone is presented as evidence for the quantum nature
of the nuclear motion. Direct observation of the tunnel level by far infrared
spectroscopy is described along with the potential energy curve for the
proton derived from the spectroscopic data.
Isotope-dependent properties are further reviewed for deuteration induced
phase transitions in tri-alkali hydrogen disulfates and similar diselenates
studied by calorimetry and neutron diffraction. Neutron diffraction at
low temperature shows a delocalized proton in ground state of these crystals.
In chromous acid an even stronger isotope effect occurs and has been discussed
in terms of the crystal structure of this particular compound. Rotational
tunneling of ammonium ions and its consequences in the phase behavior and
structure are then discussed for diammonium hexachloroplatinate and isomorphous
cubic crystals. Neutron diffraction combined with the low temperature heat
capacity has revealed that the hydrogen nuclei in these crystals are delocalized
in tori of 0.8 angstrom in diameter which surround tetrahedrally the nitrogen
atom at the center of the ammonium ion. Finally, the relation of the wave-like
properties of nuclear motion to chemical reaction and proton polarizability
is discussed.
熱測定 Netsu Sokutei 31 (3), 146-150(2004)
【解 説】
標準状態圧力の成立過程
長野八久
Historical Background of Standard State Pressure
Yatsuhisa Nagano
The history from the recognition of atmospheric pressure to the thermodynamic
standard state pressure (SSP) is reviewed. Originally, the SSP was defined
to be 101.325 kPa, one atmosphere in terms of a conventional unit, which
was based on the normal atmosphere. However, IUPAC recommended 100 kPa
as a new SSP in 1981. The normal atmosphere had not just been a standard
(prototype) of pressure unit, but a knowledge relating to the recognition
of atmospheric pressure and the normal boiling points of chemical substances.
This is the reason why the IUPAC recommendation on the SSP has not completely
prevailed even in chemistry.
熱測定 Netsu Sokutei 31 (4), 164-171
(2004)
【解 説】
遷移金属酸化物の熱起電力：強相関電子系の熱力学
寺崎一郎
Thermoelectric effects in transition-metal oxides- Thermodynamics in strongly
correlated electrons -
Ichiro Terasaki
A strongly correlated electron system is a system that the Coulomb repulsion
between electrons is too strong to hold the one-electron picture in solids.
As a result, it can exhibit superior functions to conventional solids in
which one-electron picture (band picture) is valid. Recently, thermoelectricity
due to strong correlation has attracted a keen interest, and some transition-metal
oxides, which are typical examples of strongly correlated electron system,
can be a good thermoelectric material. In this article we will review the
thermoelectric and thermodynamic properties of the transition-metal oxides
through thermopower measurement.
強相関電子系とは，電子間の強いクーロン斥力のために一電子描像が破綻した固体のことである。そのため，バンド計算の予測を凌駕する機能が発現する可能性があり，様々な分野で精力的な研究が行われている。最近，ある種の遷移金属酸化物（典型的な強相関電子系）が良い熱電変換材料であることが報じられ，強相関電子系の熱電効果が注目されている。本稿では，熱起電力から見た遷移金属酸化物の熱力学的特徴について平易な解説を試みる。また，いくつかの遷移金属酸化物の熱電効果の実験結果と解析を紹介する。
Waseda University
早稲田大学
熱測定 Netsu Sokutei 31 (4), 172-178
(2004)
【解 説】
熱分析によるペロブスカイト系酸化物材料の相関係の解析
橋本拓也
Investigation of Phase Relationship of Perovskite-related Oxide Materials
by Thermal Analyses
Takuya Hashimoto
New phases have been discovered in high functional perovskite-type oxides
with various thermal analyses and X-ray diffraction under specific conditions
such as high temperatures and high pressures. The second order phase transition
was observed in Ba2In2O5 at 1070℃ by dilatometry and quantitative DTA.
It was revealed that distortion from the ideal cubic perovskite structure
is the smallest in the phase found at higher temperatures than 1070℃ and
that this phase has the highest potential as an oxide-ion conductor among
three phases in Ba2In2O5. In addition to the three phases in BaBiO3 already
discovered by neutron diffraction measurement so far, another phase has
been observed by dilatometry and quantitative DTA in temperature range
520~620℃. The X-ray diffraction peaks indicating existence of superstructure
was observed in diffraction pattern of BaBiO3 at 600℃. Variations of enthalpy,
DH, and volume, DV, were estimated by DSC and high-temperature X-ray diffraction,
respectively. Combining Clapeyron formula, positive DH and negative DV,
phase transition under high pressure at room temperature was deduced and
confirmed by X-ray diffraction at high pressures.
各種熱分析および特殊条件下X線回折により，高機能を持つペロブスカイト系酸化物について従来報告されていない相を発見した。Ba2In2O5は910℃でブラウンミラライト型から立方晶ペロブスカイトに相転移すると報告されていたが，910～1070℃以上では歪んだペロブスカイト構造であること，および1070℃で二次相転移があり，より歪みの小さいペロブスカイト相に転移することを発見した。固体酸化物イオン伝導体としては1070℃以上の相が高いポテンシャルをもつことを明らかにした。BaBiO3は130℃，470℃で構造相転移を起こし，単斜晶から菱面体晶，立方晶へ変化すると言われていたが，高感度熱分析を実施したところ，160，520，620℃で相転移が観測され，四つの相があることを明らかにした。また520～620℃では長周期構造が存在することを明らかにした。LaCrO3は1気圧，～240℃で斜方晶から菱面体晶ペロブスカイトに，吸熱および体積収縮を伴って構造相転移することが知られている。クラペイロンの式を適用すると，高圧力下では室温でも菱面体晶が安定となることが予想された。高圧力下でのX線回折測定を実施したところ，室温，5.4
GPaでLaCrO3は菱面体晶に相転移することが確認された。
Nihon University
日本大学
熱測定 Netsu Sokutei 31 (4), 179-185
(2004)
【解 説】
熱分析による医薬品の安定性予測
上田洋一，岡本昌彦，大神泰孝，中井 清
Stability Prediction of Drug Substances using Thermal Analysis
Youichi Ueda, Masahiko Okamoto, Yasutaka Ohgami, and Kiyoshi Nakai
A stability test is one of the tests which are required the longest time
in a development of a drug. For quick release of new drugs to the market,
it is indispensable to estimate stability speedily from exact information
in preliminary stability tests, and to minimize idle time at an early developmental
stage. However, it is technically difficult to predict exactly in a short
time before a stability test, what decomposition will occur.
We developed a new stability prediction method using thermal analysis
to solve the problem. This method is very speedy; it only takes two weeks
to predict stability of a drug substance in detail. The operations are
simple; mainly thermal analysis and liquid chromatography. The method is
performed by minimum 1 mg per measurement. And total amount of sample being
necessary to predict stability is approximately 20 mg. The sample quantity
is so little that the method can be used even at an early developmental
stage when production scale is small. Furthermore, the accuracy and the
precision of prediction using the method are equivalent to or better than
those of 6-month preliminary stability tests. This method is very widely
applicable to chemical materials including pharmaceutical raw materials,
pharmaceutical intermediates, agricultural chemicals, and pesticides.
医薬品の安定性試験は，医薬品開発の中で最も長期間を要する試験の一つである。より良い医薬品を早期に上市するためには，その予備安定性試験を効率化し，より多くの精確な情報を基に保存条件を設定することが必要である。しかし，長期間の保存中に起こる各種分解を試験前の短期間で正確に把握し，安定性を確保するには技術的に難しい問題が多い。
我々は，その解決策として熱分析による新しい安定性予測法を開発した。本法は，分解から計算までの解析に要する期間が約2週間であり，迅速ある。操作は，主に熱分析とクロマトグラフ分析であり，簡便である。1測定当たり最少1
mgで行え，安定性を予測するまでに要する試料量は約20 mgである。微量で解析できるため，製造量が少ない開発初期からでも適用することができる。さらに従来6箇月間を要した予備試験と同等以上の正確さ・精度で予測することができる。本法は医薬中間体，原料，農薬および防疫薬にも適用できる高い汎用性を有する。
Sumika Chemical Analytical Service Ltd.
（株）住化分析センター
熱測定 Netsu Sokutei 31 (4), 186-193
(2004)
【解 説】
タンパク質の水和と分子体積・圧縮率
月向邦彦
Effect of Hydration on the Volume and
Compressibility of Protein Molecules
Kunihiko Gekko
This review is devoted to illustrate how the hydration of proteins is related
to their volume and compressibility. Partial volume and partial compressibility
are thermodynamic (macroscopic) quantities but they are uniquely sensitive
to the structures of proteins because the hydration and the atomic packing
(cavity) have counteractive effects on these parameters. Compressibility
data give important information on the flexibility of the native structure
and the conformation of denatured states. Viewing a protein from both the
temperature and pressure axes should lead to a new paradigm in protein
science.
タンパク質の水和や構造が，体積や圧縮率とどのように関わっているかについて解説した。タンパク質の部分体積や部分圧縮率は，巨視的な熱力学量であるにもかかわらず，溶液中のタンパク質の構造を敏感に反映している。これは，分子表面の水和と分子内キャビティーが相殺するかたちで寄与しているからである。体積や圧縮率は，高圧下でのタンパク質の挙動を理解するためだけでなく，天然状態における立体構造のゆらぎや，非天然状態のコンホメーションについても重要な情報を提供する｡温度と圧力の両軸をとおしてタンパク質を眺めることで，タンパク質の新たな描像が見えてくる。
Hiroshima University
広島大学
熱測定 Netsu Sokutei 31 (4), 194-199
(2004)
【 講 座 】
非定温速度論（2）複数素過程の場合
小澤丈夫
Non-isothermal Kinetics (2) Multiple Elementary Processes
Takeo Ozawa
The theme dealt with in this article is non-isothermal kinetics of various
processes in which multiple elementary processes are involved. Firstly
fundamental equation of non-isothermal nucleation and growth process is
derived and it is compared with isothermal fundamental equation.
From the fundamental equation, method of kinetic analysis of data by constant
rate heating or cooling is derived. Theoretical considerations are also
made for parallel competitive reactions and consecutive reactions. For
the former some simple relations useful to elucidate the process can be
derived, but for the latter such a simple useful relation cannot be found,
but a fundamental equation is derived for specific cases. Finally usefulness
of temperature oscillation for analyzing reversible processes is discussed
together with its application to a reaction of a single elementary process.
複数の素過程が関与する様々な過程の非定温速度論ついて考察した。最初に，核が発生しそれが成長する過程の非定温速度論の基本式を導き，定温条件の速度式と比較した。定速の加熱あるいは冷却の場合速度論解析が可能である。並進反応や続発反応についても同様に考察した。並進反応については不充分ではあるが解析に利用できる簡単な関係が見出される。続発反応については，特定の場合に限り基本式が書けるが，有用ではない。温度振動の可逆的過程の速度論解析への応用についても解説し，合わせて非可逆反応への適用についても考察した。
元 千葉工業大学
熱測定 Netsu Sokutei 31 (5), 212-216
(2004)
【 特別寄稿 】
日本熱測定学会の発展を振り返って
小澤丈夫
Historical Review on Development of the Japan Society of Calorimetry and
Thermal Analysis
Takeo Ozawa
History of the Japan Society of Calorimetry and Thermal Analysis is described
since the first Japanese Calorimetry Conference in 1965. The society was
established in 1969, and since then various activities have been made.
They are the conferences, the journal, organization of international conferences,
joint meetings with the Japan Society of Thermophysical Properties and
miscellaneous activities such as publication, workshops, group activities
and short courses for beginners. Statistical data are also reviewed. Finally
further development of the society in the future is discussed.
日本熱測定学会の歴史が，1965年の第一回熱測定討論会から記述されている。この学会は1969年に創設され，以後様々な活動を行ってきた。それは，討論会の開催，会誌発行，国際会議の組織，日本熱物性学会との合同会議の開催などであり，出版，ワークショップ，グループ活動や初心者向け講習会なども含まれる。統計データも検討された。最後に将来の学会の発展が論じられている。
元千葉工業大学教授
熱測定 Netsu Sokutei 31 (5), 217-226
(2004)
【 特別寄稿 】
熱測定40年の回顧と展望
菅 宏
A View of Thermal Measurements in JSCTA
Hiroshi Suga
Developments of microcalorimeters for combustion, heat capacity, and solution
calorimetry that have been done in our Society over the past four decades
are surveyed. Unique experimental results obtained for several equilibrium
and nonequilibrium systems are reviewed in some details. Molecular
systems are the main of these topics, hoping that the description reflects
the development of other fields in our Society, including metals, inorganic
and organic substances, synthetic polymers, and biological materials. Some
remarks for further works based on personal experiences are given in this
article.
主として分子集合体を例にとり，過去40年間にわたって筆者の身の回りで見聞したユニークな装置の発展や特長的な実験結果を述べてきた。鉱物，金属，無機化合物，合成高分子，医薬品，生体物質，その他の分野でも大きな進展があるが，本記述が学会全体の発展過程を映し出す鏡となることを期待したものである。非平衡凍結系や不可逆過程，生体系への実験的研究や更なる熱量計のミクロ化への大きな期待についても触れた。
professor Emeritus, Osaka University
大阪大学名誉教授
熱測定 Netsu Sokutei 31 (5), 227-233
(2004)
【 論 文 】
Thermodynamic Investigations and Characterization of Some Alloys in Ternary
Pb-Au-Bi System
Dragana Zivkovic, Biserka Trumic, and Zivan Zivkovic
The results of thermodynamic investigations and characterization of some
alloys in ternary Pb-Au-Bi system are presented in this paper. Partial
and integral molar quantities were determined in the temperature range
of 873～973 K, based on the comparative thermodynamic analysis done experimentally
using Oelsen calorimetry and analytically using Redlich-Kister-Muggianu
model. Characterization of chosen lead-based ternary alloys were done using
DTA, XRD and SEM analysis.
University in Belgrade
熱測定 Netsu Sokutei 31 (5), 234-240
(2004)
【解 説】
両親媒性ブロック共重合体が形成するメゾスコピックスケール規則構造
吉田博久
Ordered Structures in Mesoscopic Scale of Amphiphilic Block Copolymers
Hirohisa Yoshida
The nano-scale ordered structure and phase transitions of amphiphilic di-block
copolymers consisted of hydrophilic poly(ethylene oxide) and hydrophobic
poly(methacrylate) derivatives having azobenzene (AZO) moieties as ester
groups, p(EO)mpMA(AZ)n, were reviewed. Hexagonal-packed PEO cylinder structure,
caused by micro phase separation of amphiphilic di-block copolymers were
selectively formed in wide copolymer content and temperature ranges for
p(EO)mpMA(AZ)n. The order of hexagonal cylinder depended strongly on the
annealing temperature, however, slightly on copolymer content. The series
of p(EO)mpMA(AZ)n showed four endothermic transitions on heating. From
the simultaneous DSC-XRD measurements, four phase transitions were assigned,
in the order of the low to high temperatures, as the melting of PEO, the
melting of AZO moieties, the transition from smectic C to smectic A and
the isotropic transitions, respectively. AZO moieties acted as megenic
groups. The formation of hexagonal cylinder structure was expected as the
results of entropy loss casued by liquid crystalline formation. The director
orientation of the liquid crystalline state would be the key in producing
the single crystalline nano-scale ordered hexagonal cylinder structure.
ポリエチレンオキシド（PEO）とアゾベンゼン（AZO）をエステル側鎖に持つポリメタクリル酸エステルから構成する液晶型両親媒性二元共重合体，p(EO)mpMA(AZ)n，のナノ規則構造と相転移を概説した。p(EO)mpMA(AZ)nは広い組成ならびに温度範囲で，PEOシリンダーが六方晶配列したナノ構造を示した。低温側からPEOの融解，AZOの融解，スメクチックAからCへの転移，等方性転移の4種類の転移が観察された。ナノ規則構造の秩序と配列は熱処理温度と液晶配向の影響を受ける。
Tokyo Metroporitan University
東京都立大学
熱測定 Netsu Sokutei 31 (5), 241-248
(2004)
【 講 座 】
高分子のDSCとTMA
十時 稔
DSC and TMA of High Polymers
Minoru Todoki
Fundamentals of apparatuses and analyses of DSC and TMA were described
for polymeric materials.
In apparatuses, measuring principles were explained firstly and secondly
the two confusing problems of DSC, i.e., why two types of DSC, heat-flux
DSC and power-compensation DSC, do still exist, and why their charts adopt
opposite direction for Y-axis were elucidated from their historical and
measuring aspects.
In analyses, enthalpy and volume-temperature relationships of low molecular
weight substance were reviewed and apparently unusual behaviors of polymers
were pointed out. Finally nanosize behavior of polymer crystals was emphasized
as the most important topic among them and their zero-entropy-production
melting was exemplified for nylon 6 fibers, comparing with their conventional
melting.
高分子材料のDSCとTMAについて，装置と解析の両面から基礎的な点に主眼を置いてのべた。装置面では，測定原理のみならず，現在なぜ熱流束型DSCと入力補償型DSCが存在しているのか，なぜ両DSCでチャートの吸発熱が逆になっているのか，についても歴史的なことを交えてのべた。解析面では，DSC・TMA曲線の解釈の基礎となる低分子物質の状態図について復習したのち高分子の特異性を列挙し，これらも結果的にはこの状態図の枠内に納まる現象であるとした。最後に，この特異性の中で最も重要と考えられる高分子結晶のナノサイズ性を取り上げ，結晶サイズ固有の融点の実測例を示した。これは通常のDSCで観測される高分子の融点とは何か，という根本問題の提起であり，それに対する答えでもある。
Shiga Women's Junior College
元（株）東レリサーチセンター，滋賀女子短期大学