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The heat capacity of [Fe(2-pic)3]Cl2·C2H5OH Crystal (2-pic: 2-picolylamine) has been measured with an adiabatic calorimeter between 13 and 315 K. Two phase transitions centered at 114.04 and 122.21 K were observed. This finding accords with recent prediction of possible existence of two-step spin-conversion (H. Köppen et al., Chem. Phys. Lett., 91 (1982) 348). The total transition enthalpy and entropy amounted to ΔH = 6.14 kJ mol?1 and ΔS = 50.59 J K?1 mol?1. The transition entropy consists of the magnetic contribution (13.38 J K?1 mol?1), the orientational order-disorder phenomenon of the solvate ethanol molecule (8.97) and the change in the phonon system, in particular the change in stretching and deformation vibrations of the metal-ligand (28.24). 相似文献
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Masanori Yoshikawa Michio Sorai Hiroshi Suga Syŭzŏ Seki 《Journal of Physics and Chemistry of Solids》1983,44(4):311-321
Heat capacity measurements have been made for six kinds of specimens prepared by different methods. Among them, Sample A exhibited a A-type ferromagnetic pahse transition at 1.347 K and a Schottky-type anomaly due to the zero-field splitting around 9K. The total entropy and enthalpy were (11.05 ± 0.04) J K?1mol?1 and (97.0 ± 0.4) J mol?1, respectively. Sample B exhibited a Sehottky-type anomaly around 0.4 K due to the ferro-magnetic dimeric coupling with as well as the Schottky-type anomaly at 9K. The total magnetic entropy and enthalpy were (11.45 ± 0.03) JK?1 mol?1 and (93.8 ± 0.8) J mol?1, respectively. The remaining samples are simple mixtures of the λ-type modification and the dimeric modification. Irrespective of the magnetic behavior at low temperatures, all the samples showed a non-magnetic first-order phase transition around 270 K. The heat capacity and entropy of this phase transition have been accounted for in terms of the Frenkel theory of heterophase fluctuation. Construction of an adiabatic-type calorimeter workable between 1.5 and 393 K has been also presented. 相似文献
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Michio Sorai Kazuya Saito Tadahiro Nakamoto Mayumi Ikeda Yuri G. Galyametdinov Irina Galyametdinova Rudolf Eidenschink Wolfgang Haase 《Liquid crystals》2003,30(7):861-869
The heat capacity of the cubic mesogen ACBC(16) was measured between 16 and 500 K by adiabatic calorimetry. As well as the known condensed phases, a new crystalline phase was found to undergo a glass transition at around 165 K. Phase transitions between crystal, SmC, cubic, and isotropic liquid phases took place at 399.16, 431.15, and 474.30 K, respectively. As in the case of ANBC, a broad hump was observed in the heat capacity of the isotropic liquid phase. The first order nature of the SmC-cubic phase transition was confirmed for the first time by the observation of supercooling of the cubic phase. The broad hump in the isotropic liquid phase was shown to extend to a low temperature side if the isotropic liquid was supercooled, suggesting that the event occurring at the hump is not directly related to the cubic-isotropic liquid phase transition. 相似文献
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Gerald R. Van Hecke Tadahiro Nakamoto Todd G. Clements Michio Sorai 《Liquid crystals》2003,30(7):831-837
The heat capacity of the metallomesogen purple cobalt stearate Co(O2CC17H35)2 has been measured by adiabatic calorimetry at temperatures between 16 and 420 K. This compound exhibits two crystalline phases (low temperature Cr2 and high temperature Cr1 phases), mesophase (M phase), and isotropic liquid (I phase). A third crystalline phase Cr3, which is entirely metastable with respect to all the others, is suggested by DSC studies. The Cr2-to-Cr1, Cr1-to-M, and M-to-I phase transitions occurred at 362.1, 380.9, and 400.4 K, respectively. The enthalpy and entropy gains at these phase transitions were determined. The mesophase is either smectic A or nematic. 相似文献
5.
Abstract The heat capacities of the title compound (C3H11,O—C6H4,- CH=N—C6H4,—C4H9, abbreviation 5O ? 4) with a purity of 99.92 mole percent have been measured with an adiabatic-type calorimeter between 11 and 393 K. The transition temperature and the enthalpy and entropy of phase transition for stable crystal → SG, SG → N and N → isotropic liquid were T c = 299.69 K/ΔH = 22.68 kJ mol?1/ΔS = 75.70 JK?1 mol?1, 325.72/7.11/21.79 and 342.48/1.78/5.22, respectively. The crystal which melts at 285.5 K is a metastable modification. The SA phase hitherto reported in between SG and N does not exist. The glassy So state was realized by rapid cooling of the specimen from the So phase. The molar enthalpy of the glassy SG state at 0 K was by (10.1±0.1) kJ mol?1 higher than that of the stable crystalline state and the residual entropy of the glassy state was (9.40±0.83) JK?1 mol?1. The relaxational heat-capacity anomaly was observed from as low as 100 K and double glass transition phenomenon occurred around 200 K; a quite unusual phenomenon which has never been observed for the glassy states of nematic and cholesteric liquid crystals. The present results give a fair evidence that the unusual glass transition phenomenon previously found for the SG state of 6O?4 (a homologous compound) is not exceptional at all but common to the smectic glasses; at least common to the glassy SG states. Two possible origins responsible for the double glass transitions have been discussed. 相似文献
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Kazuya Saito Yasuhiro Takahashi Michio Sorai 《Journal of Polymer Science.Polymer Physics》2000,38(12):1584-1588
The heat capacity of crystalline poly(p‐phenylenebenzobisoxazole) was measured below room temperature by adiabatic calorimetry. The standard thermodynamic functions (enthalpy, entropy, and Gibbs energy) were established and tabulated. The temperature dependence of the heat capacity was compared with those of polyethylene and poly(p‐phenylene), with attention paid to the low dimensionality of the systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1584–1588, 2000 相似文献
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Studies on the magnetic properties of the molecular antiferromagnetic material {N(n-C5H11)4[MnIIFeIII(ox)3]}∞, carried out by various physical techniques (AC/DC magnetic susceptibility, magnetization, heat capacity measurements and Mössbauer spectroscopy) at low temperatures, have been presented. Different experimental observations complement each other and provide a clue for the observation of an uncompensated magnetization below the Néel temperature and short-range correlations persisting high above TN. It is understood that the honeycomb layered structure of the compound contains non-equivalent magnetic sub-lattices, (MnII–ox–FeIIIA–...) and (MnII–ox–FeIIIB–...), where different responses of the FeIIIA and FeIIIB spin sites towards an external magnetic field might be responsible for the observation of the uncompensated magnetization in this compound at T < TN. The present magnetic system is an S = 5/2 2-D Heisenberg antiferromagnet system with the intralayer exchange parameter J/kB = −3.29 K. A very weak interlayer exchange interaction was anticipated from the spin wave modeling of the magnetic heat capacity for T < 0.5TN. The positive sign of the coupling between the layers has been concluded from the Mössbauer spectrum in the applied magnetic field. Frustration in the magnetic interactions gives rise to the uncompensated magnetic moment in this compound at low temperatures. 相似文献
10.
Akane Sato Mizuho Okada Kazuya Saito Michio Sorai 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(5):564-565
In the crystal structure of the title charge‐transfer complex, namely trans‐stilbene–2,2′‐(2,3,5,6‐tetrafluorobenzene‐1,4‐diylidene)propanedinitrile (1/1) (trans‐STB–TCNQF4), C14H12·C12F4N4, the planar STB and TCNQF4 molecules are stacked alternately. The structure is not isostructural with that of STB–TCNQ. No anomaly was found in the displacement parameters of any atoms, while the bond length of the central C=C moiety was shorter than the corresponding bond in ethylene. This suggests that the central C=C moiety of the STB molecule vibrates with a large amplitude, similar to the case in free STB and STB–TCNQ. 相似文献