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41.
It is shown that new parametersX can be defined such that the heat capacity CxT(S/T)x is negative, even when the canonical ensemble [i.e., at fixed T=(U/S)Y and YX] is stable. This implies an extension of the classical theory of polytropes from ideal gases to general fluids. As examples of negative heat capacity systems we treat blackbody radiation and general gas systems with nonsingular T. For the case of a simple ideal gas we even exhibit an apparatus which enforces a constraint X(p, V)=const that makes Cx<0. We then show that it is possible to infer the statistical mechanics of canonicallyunstable systems-for which even the traditional heat capacities are negative-by imposing constraints that stabilize the associated noncanonical ensembles. Two explicit models are discussed. 相似文献
42.
双电层相互重叠时蒙脱胶体表面阴离子的负吸附 总被引:2,自引:0,他引:2
本文用Ag-AgCl电极判断平衡,测定双电层处于不同重叠程度下肢体表面阴离子的负吸附量Γ.结果表明,胶体表面双电层相互重叠程度可由两胶体表面间的中点电位φd与外Helmhotz面处的电位φd之比表征;阴离子负吸附随双电层重叠程度和电解质浓度的增加而显著减小. 相似文献
43.
The refractive index, n
D
, and density, ρ, of binary mixtures of monoalcohols + water, have been measured at a temperature of 298.15,K and atmospheric pressure. The variation of the refractive indices of these solutions has also been determined with temperature in the range T = (278.15 to 338.15) K and atmospheric pressure. A comparative study has been made of the refractive indices obtained experimentally and those calculated by means of the Lorentz-Lorenz [Theory of Electrons, Dover Phoenix (1952)] and Gladstone-Dale relations [Trans. R. Soc. London 148:887–902 (1858)]; in all cases, the Gladstone–Dale equation was seen to afford values similar to those obtained experimentally. Calculations have been made of the excess molar volumes, V
E, and the molar refraction deviations, ΔR, of these mixtures and the differences between the experimental values for refractive index and those obtained by means of the Gladstone–Dale equation. Values of V
E were compared with others in the literature. In all cases the V
E values were negative, and in all cases, except in the methanol + water, ΔR showed a maximum for x = 0.8. 相似文献
44.
The rheological properties of the aqueous mixtures of cationic-anionic surfactants, both in single-phase systems and in aqueous two-phase systems, have been studied. Bizarre rheological properties —negative thixotropy, viscoelasticity and hihg viscosity of shear rate dependent at relatively low concentration — have been observed. An unusual viscosity change, that is, viscosity lowering with increasing concentration, was obtained. The negative thixotropy might be due to the existence of lamellar or sheet-like micelles, viscoelasticity might be induced by rodlike and lamellar or sheet-like micelles, the high viscosity might be a consequence of the formation of network by long rodlike micelles and the concentration-induced viscosity lowering could be interpreted in terms of the decrease of micellar dimensions with concentration. 相似文献
45.
46.
The absorption of millimeter electromagnetic radiation (v=1.4, 1.71, and 5 cm−1) by aqueous solutions of glycine (pH 6.1–6.2) in the concentration range of 0.5–2.5 mol L−1 was measured. It was found that the absorbing ability of the water present in the solutions, is higher than that of pure
water. This phenomenon is explained by the presence of a center of negative hydration in the structure of the glycine zwitterion,
which results in an increase in the rotational mobility of water molecules immobilized in the hydrate shell of the glycine
zwitterion.
For Part 5, see Ref. 1.
Deceased.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1305–1307, July, 1997. 相似文献
47.
48.
紫外吸收温差光谱法及其应用 总被引:1,自引:0,他引:1
用温差光谱法观察系列化合物的紫外吸收温差谱,发现温差谱具有很强的特征性,具有π键的富勒烯C60的温差谱峰为负值,负峰的强度样品温差增大而负荷增大,负峰的峰位无明显移。 相似文献
49.
本文回顾了在羰基引发剂的作用下烯烃单体光引发聚合的最新机理。报道了有关多种当前通用的新型羰基引发剂的光物理和光化学的近期工作,其中包括 UV 吸收,发光光谱和闪光光解的研究。还报道了油溶性引发剂对丙烯酸丁酯的光聚合效应。证明油溶性引发剂实质上是经过三重态来起作用,其中包含一个从溶剂中攫取氢的引发步骤。对于硫杂蒽酮衍生物来说,它们从叔胺接受电子的能力及其光聚合效应之间有一定的关系。从闪光光解获得的证据说明在这种情况下存在着自由基阴离子,但是基于二苯酮和苯基酮的引发剂则没有。预料后者直接从胺攫氢是通过三重态羰基或是引发剂的自由基。有证据表明联苯甲酰主要是通过光裂解来起作用。水溶性硫杂蒽酮引发剂的作用主要是经过单重态,其中包含引发时攫氢一步。在这种情况下,自由基的形成不受氧的影响。 相似文献
50.
Dissociative and nondissociative electron attachment in the electron impact energy range 0–14 eV are reported for SOF2 SOF4, SO2F2, SF4, SO2, and SiF4 compounds which can be formed by electrical discharges in SF6. The electron energy dependences of the mass-identified negative ions were determined in a time-of-flight mass spectrometer. The ions studied include F– and SOF
2
–*
from SOF2; SOF
3
–
and F– from SOF4; SO2F
2
–*
, SO2F–, F
2
–
, and F– from SO2F2; SF
4
–*
and F– from SF4; O–, SO–, and S– from SO2; and SiF
3
–
and F– from SiF4. Thermochemical data have been determined from the threshold energies of some of the fragment negative ions. Lifetimes of the anions SOF
2
–*
, SO2F
2
–*
, and SF
4
–*
are also reported. 相似文献