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21.
Heat capacities (Cp) of solid benzene, biphenyl,p-terphenyl,p-quaterphenyl, and poly-p-phenylene were analyzed using the ATHAS Scheme of computation. The calculated heat capacities based on approximate vibrational spectra of solid benzene and the series of oligomers containing additional phenylene groups were compared to experimental data newly measured and from the literature to identify possible additional large-amplitude motion. The skeletal heat capacity was fitted to the Tarasov equation to obtain the one- and three-dimensional vibration frequencies 1 and 3 using a new optimization approach. Their relationship to the number of phenylene groupsn is: 1=426.0–150.3/n; and 3=55.4+81.8/n. Except for benzene, the quantitative thermal analyses do not show significant contributions from large-amplitude motion below the melting temperatures.This work was financially supported by the Div. of Materials Res., NSF, Polymers Program, Grant # DMR 90-00520 and Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U. S. Department of Energy, under contract number DE-AC05-96OR22464. 相似文献
22.
The technique of temperature waves to measure the complex thermophysical characteristics of materials has been proposed. The relations for the moduli and arguments of these characteristics for the case of plane temperature waves have been calculated. The temperature dependences of the moduli and arguments of complex thermophysical characteristics of polyvinylacetate (PVAc) at different frequencies and also the temperature dependences of its vibrational and configurational heat capacities have been determined. It has been shown that the vibrational heat capacity of PVAc in the region of softening grows sharply and its configurational heat capacity goes through a peak. The segmental mobility has been found to affect the heat transfer in the polymer in an ambivalent way causing both a decrease and increase of thermal conductivity.
Zusammenfassung Zur Bestimmung der komplexen thermophysischen Eigenschaften von Stoffen wurde eine Temperaturwellentechnik vorgeschlagen. Für den Fall zweidimensionaler Temperatur-wellen wurden die Verhältnisse von Moduli und Argumenten dieser Eigenschaften berechnet. Die Temperaturabhängigkeit von Moduli und Argumenten der komplexen thermophysischen Eigen-schaften von Polyvinylacetat (PVAc) bei verschiedenen Frequenzen und auch die Temperatur-abhängigkeit seiner Vibrations- und Konfigurations-Wärmekapazitäten wurden bestimmt. Es wurde gezeigt, daß die Vibrations-Wärmekapazität von PVAc im Erweichungsbereich scharf zunimmt und die Konfigurations-Wärmekapazität durch einen Peak geht. Man fand, daß die Segment-Mobilität den Wärmetransport im Polymer auf eine ambivalente Weise beeinflußt, in dem die Wärmeleit-fähigkeit entweder gesenkt oder angehoben wird.相似文献
23.
Using the Picker flow microcalorimeter, excess heat capacities have been obtained at 25°C throughout the concentration range for 2,2-dimethylbutane,n-hexane, and cyclohexane each mixed with a series of hexadecane isomers of increasing degrees of orientational order, as determined by depolarized Rayleigh scattering. The isomers are 2,2,4,4,6,8,8-heptamethylnonane, 6-, 4-, and 2-methylpentadecane, andn-hexadecane. Thec
p
E
values are negative, increasing rapidly in magnitude with increase of orientational order, and are not predicted by the Prigogine—Flory theory which neglects order. Values ofc
p
E
are obtained at 10, 25, and 55°C for cyclohexane +6-, 4-, and 2-methylpentadecane which with other literature data lead to the temperature dependence of the thermodynamic excess functions for cyclohexane solutions of the five C16 isomers. The excess enthalpy and entropy vary with the C16 isomer and with temperature, but the corresponding variation of the excess free energy is small, indicating a high degree of enthalpy-entropy compensation. This is consistent with a rapid decrease with temperature of orientational order in the C16 isomers. 相似文献
24.
25.
Kulova T. L. Karseeva E. I. Skundin A. M. Kachibaya E. I. Imnadze R. A. Paikidze T. V. 《Russian Journal of Electrochemistry》2004,40(5):494-499
A series of compounds with the general formula LiMn2 - x - y
Cr
x
Ni
y
O4, where x + y = 0.05, 0.5, or 1.0, is synthesized. It is shown that all these compounds are pure-phase spinels with parameter aequal to 0.8193-0.8236 nm. Doping a stoichiometric lithium-manganese spinel simultaneously with chromium and nickel makes the spinel structure stable. The initial specific capacity of a spinel depends on its doping degree. Doping LiMn2O4 with chromium and nickel simultaneously at an Mn : Cr : Ni ratio of 195 : 3 : 2 raises the spinel's specific capacity and reduces the cycling degradation. The change in the discharge capacity of LiMn1.95Cr0.03Ni0.02O4 electrodes cycled at 20, 0, and -14°C is determined. 相似文献
26.
27.
Using a precise technique of scanning microcalorimetry the heat capacity differences between water and dilute aqueous solutions of ethanol, n-propanol, n-butanol and n-pentanol were measured from 5 to 125°C and the partial molar heat capacities of these substances in water were determined. It was found that the heat capacity increment for alcohol disolved in water is proportional to the number of the-CH
2
–
groups and decrease with a temperature increase. The heat capacity increment of hydration of non-polar groups is shown to be positive and large at room temperature and decreases in magnitude as the temperature increases. In contrast, the heat capacity increment of hydration of polar groups is negative at room tempreature and increases as the temperature increases. From the temperature dependence of the heat capacity increment one can assume that the water molecules solvated by the non-polar groups of the alcohols behave in a non-cooperative manner. 相似文献
28.
Monuron (C9H11ClN2O; N,N-dimethyl-N′-(4-chlorophenyl) urea, CAS 150-68-5) was synthesized and the heat capacities of the compound were measured in the temperature range from 79 to 385 K with a high precision automated adiabatic calorimeter. No phase transition or thermal anomaly was observed in this range. The enthalpy and entropy data of the compound relative to the reference temperature 298.15 K were derived based on the heat capacity data. The thermodynamic properties of the compound were further investigated through DSC and TG analysis. The melting point, the molar enthalpy, and entropy of fusion were determined to be 447.6±0.1 K, 29.3±0.2 kJ mol−1, and 65.4 J K−1 mol−1, respectively. 相似文献
29.
Russell G. Ross 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):227-233
The thermal conductivity and the heat capacity per unit volumec
p
have been measured for the urea-hexadecane inclusion compound using the transient hot-wire method. Measurements were made under isobaric conditions at a pressure of 0.1 GPa and in the temperature range of 100–300 K. There was evidence for a phase transition at a temperature of about 160 K, in reasonable agreement with previous work. For the high-temperature phase was independent of temperature within ±1%. The low-temperature phase showed a weak temperature dependence, with (d In/d InT)
p
= –0.13. It was inferred that interaction between acoustic phonons and low-frequency vibrational excitations of the guest molecules made a major contribution to the thermal resistivity. For the quantityc
p
a weak maximum was observed in the region of the phase transition temperature.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
30.
Scanning calorimetric methods permit determination of heat capacities at high temperatures up to 1600°C. For disk systems
with power compensation application limits are in order of 700°C, and for cylindrical systems with electrical calibration
up to 1000°C. For the high temperature range above 1000°C DSC plates and a cylindrical calorimetric systems based on the CALVET
principle ('MULTI HTC’) are known. For cylindrical calorimetric systems the precision of the Cp data is between 2 and 5% even
at high temperatures without any requirements on the kind and shape of samples. These results are better than data provided
by DSC plate systems.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献