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41.
A. K. Galwey 《Journal of Thermal Analysis and Calorimetry》2005,82(2):423-437
Summary A representational model, proposed to account for the physical changes that accompany the melting of alkali halides, was described
in Part 1 [1]. The liquid is portrayed as undergoing continual dynamic structural reorganization of its constituent ions between
individual small domains, zones of various regular, crystal-type arrays. These alternative arrangements are stabilized by
the enthalpy of melting, which, in liquids, relaxes the restriction for solids that only the single, most stable, crystal
structure can be present. The dynamic character of the melt accounts for its fluid character and the loss of long-range order
[1, 2]. This model is extended here to consider the phase diagrams of binary, common ion, alkali halide mixtures comprehensively
reviewed in [3]. Factors determining whether each of these yields a eutectic, or a solid solution, on cooling are discussed
and several trends in the 70-phase diagrams are identified. Eutectic formation, involving maintenance of the liquid state
below the melting points of the pure components, is ascribed to the participation, in an extended dynamic equilibrium, of
additional domains having the regular structures characteristic of double salts. The known crystalline double binary halides
[3], Li/Cs or Rb/F, Cl, Br or I, melt at temperatures well below those of the simpler pure component salts. It is concluded
that the set/liq model for melting, proposed in [1, 2], accounts for some important properties of the phase diagrams presented
in [3]. 相似文献
42.
Differential
scanning calorimetry (DSC) is a thermal analytical tool for preformulation
studies. Extrapolated melting temperature (TP)
and heat of fusion (ΔHf)
can be used as parameters for optimizing the DSC performance. Two model pharmaceuticals
acetaminophen and nicotinamide are used in this study. Using a factorial design
for the experimental model and matrix analysis the results, the effect of
sample mass, heating rate and the nitrogen flow rate were evaluated on the
ΔHf values
and TP values. Two
levels for each of the procedural variables were used as a balanced experimental
design with two sample sizes, two heating rates and two nitrogen flow rates.
It was found that the change in the heating rate caused significant changes
in the ΔHf
values but not the Tp
values for acetaminophen. However, no significant effect was found for the Tp value but ΔHf value was affected to a
certain extent for nicotinamide. 相似文献
43.
The enthalpies of sublimation and fusion and triple-point temperatures of 2-bromo-. 3-bro-mo- and 4-bromobenzoic acids have been determined precisely by sublimation calorimetry, drop calorimetry and differential thermal analysis. The measurements of sublimation enthalpy of the three acids were made at 333, 348 and 363 K, respectively, using a Tian-Calvet microcalorimeter equipped with Knudsen effusion cells. The derived standard molar enthalpies of sublimation at 298.15 K are (95. 94±0. 41), (99. 20± 0.18), and (103. 08±0. 59) kJ · mol-1for the 2-bromo-, 3-bromo- and 4-bromobenzoic acids, respectively. In addition, the saturated vapour pressure of these compounds was also calculated on the basis of the sublimation experiments. The enthalpy of fusion, the triple-point temperatures and the mole fraction purities of the samples of the investigated substances were measured using the mean temperature version DTA apparatus developed by the CTM of the CNRS in Marseille. The triple-point temperature and the 相似文献
44.
45.
The problem of minimizing a nondifferential functionx f(x) (subject, possibly, to nondifferential constraints) is considered. Conventional algorithms are employed for minimizing a differential approximationf
off (subject to differentiable approximations ofg). The parameter is adaptively reduced in such a way as to ensure convergence to points satisfying necessary conditions of optimality for the original problem.This research was supported by the UK Science and Engineering Research Council, the National Science Foundation under Grant No. ECS-8121149, and the Joint Services Electronics Program, Contract No. F49620-79-C-0178. 相似文献
46.
47.
Measurement of the degree of crystallinity of the polymer matrix in a composite is complicated by the presence of the reinforcing additive. This is particularly the case in APC-2 in which as much as 70% can be carbon fibre. A First Law procedure, developed for determining the degree of crystallinity of PEEK, which involves direct measurement of the enthalpy changes associated with melting, crystallization and heat capacity changes, has found to be an effective method for the determination of the crystallinity of the PEEK matrix. The procedure has been applied to carbon fibre and glass fibre PEEK composites. 相似文献
48.
Comment on papers by K. Shanahan that propose to explain anomalous heat generated by cold fusion 总被引:1,自引:0,他引:1
Edmund Storms 《Thermochimica Acta》2006,441(2):207-209
Dr. Shanahan has published two papers (Thermochim. Acta 428 (2005) 207, Thermochim. Acta 382 (2002) 95) in which he argues that excess heat claimed to be produced by cold fusion is actually caused by errors in heat measurement. In particular, he proposes that unrecognized changes in the calibration constant are produced by changes in the locations where heat is being generated within the electrolytic cell over the duration of the measurement. Because these papers may lend unwarranted support to rejection of cold fusion claims, these erroneous arguments used by Shanahan need to be answered. 相似文献
49.
T.D. Klots P. Devlin W.B. Collier 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1997,53(14):2445-2456
Infrared and Raman measurements for benzimidazole are presented and discussed, including its argon-matrix infrared spectrum. To assist in the assignment, benzimidazole's harmonic force fields for the 321G* and 631G* levels were scaled by scaled factors derived by fitting the respective computed force fields of other indene derivatives to previously reported experimental vibrational frequencies. Comparison to the best set of experimental wavenumbers, usually taken from the matrix, shows mean 321G* and 631G* deviations of 7.0 and 5.8 cm−1 for the planar modes, and 14.0 and 6.8 cm−1 for the nonplanar modes, respectively, with much of the error residing in imino-hydrogen group modes. Standard entropies are derived with the matrix wavenumbers and the methods of statistical mechanics. An attempt to determine standard entropies by calorimetric methods was unsuccessful. The triple-point temperature Ttp and enthalpy of fusion Δ1crHm only are reported. 相似文献
50.
In recent decades, emotion recognition has received considerable attention. As more enthusiasm has shifted to the physiological pattern, a wide range of elaborate physiological emotion data features come up and are combined with various classifying models to detect one’s emotional states. To circumvent the labor of artificially designing features, we propose to acquire affective and robust representations automatically through the Stacked Denoising Autoencoder (SDA) architecture with unsupervised pre-training, followed by supervised fine-tuning. In this paper, we compare the performances of different features and models through three binary classification tasks based on the Valence-Arousal-Dominance (VAD) affection model. Decision fusion and feature fusion of electroencephalogram (EEG) and peripheral signals are performed on hand-engineered features; data-level fusion is performed on deep-learning methods. It turns out that the fusion data perform better than the two modalities. To take advantage of deep-learning algorithms, we augment the original data and feed it directly into our training model. We use two deep architectures and another generative stacked semi-supervised architecture as references for comparison to test the method’s practical effects. The results reveal that our scheme slightly outperforms the other three deep feature extractors and surpasses the state-of-the-art of hand-engineered features. 相似文献