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991.
992.
Mixtures composed of amides and electrolytes exhibit interesting properties such as viscoelastic behaviour and a megavalue of the dielectric constant. In order to improve the dielectric properties, the authors are investigating a large number of molten mixtures of CF3COONa with different types of amides, including the ternary system sodium trifluoroacetate-chloroacetamide-acetamide. The experimental measurements showed that the ternary mixtures are thermally unstable. A yellow oily product is formed; this was purified and tested by means of IR and NMR techniques. The formula and the kinetic mechanism are proposed. 相似文献
993.
O. Kindel F. J. Herrmann L. Schmidt 《Journal of Radioanalytical and Nuclear Chemistry》1994,183(2):219-224
By simulation experiments with a 10–5 mol/l solution of iodododecane labeled with131I in n-dodecane the influence of various materials and conditions, which are possible in nuclear fuel reprocessing, has been investigated. The formation of decomposition products was detected via HPLC with a radioactivity monitor. By means of252Cf plasma-desorption mass spectrometry (PDMS) the decomposition products were identified. It was found that a temperature of 100°C favored the formation of iodoalkanes with chain lengths of C1 to C11. The presence of TBP(tri-n-butyl-phosphate) accelerated the decomposition of iodododecane. In pure TBP only iodobutane was formed as a decomposition product. 相似文献
994.
The soft mode dielectric response of three ferroelectric chiral smectic C* substances is studied in the vicinity of the smectic C*-smectic A* phase transition. For some substances the soft mode dielectric strength exhibits a pronounced anomaly in the C* phase just below the phase transition. We show how this anomaly can be systematically correlated with a corresponding anomaly in the experimentally determined ratio of spontaneous polarization over tilt. By comparing the experimental results with the theoretical predictions of an extended Landau model, we demonstrate how the crossover behaviour of the system can be interpreted as being the consequence of the presence of a biquadratic coupling between tilt and polarization in the Landau free-energy of the system. 相似文献
995.
Philippe Quevauviller Rob Ritsema Roberto Morabito Wilfried M. R. Dirkx Salvatore Chiavarini Jos M. Bayona Olivier F. X. Donard 《应用有机金属化学》1994,8(6):541-549
Biogeochemical pathways of tin species in the environment are still controversial, e.g. with regard to methylation and transmethylation phenomena, owing to the fact that the identification of methylated tin-compounds is often difficult. The previous tentative identification of a mixed methylbutyltin compound in sediment and biological samples by GC/AAS after hydride generation gave an illustration of this problem. This compound was previously identified in sediments by other authors and also suspected to occur in a contaminated sediment sample from the Boyardville Marina, France. The retention time obtained by GC/AAS corresponded to the actual retention time of a mixed methylbutyltin calibrant. However, additional checks demonstrated that the compound detected was actually monophenyltin. This evidence was produced by a thorough analysis of a selected sediment sample by alternative techniques such as GC/AAS and GC/AES after pentylation, GC/FPD and GC/MS. The results presented highlight the need for a full identification of compounds to avoid mis-interpretation. 相似文献
996.
Oxyethylene macrocyclic compounds (crown-ethers) act as ligands of intracrystalline cations of certain layered silicates as montmorillonites. Stable intercalation materials are formed which are used to prepare organic-inorganic membranes by encapsulating these intercalation compounds with a poly-butadiene thin coating. Electrochemical Impedance Spectroscopy (EIS) is used to study the resulting composite membranes in contact with aqueous electrolytes. From the impedance plots, the ionic resistance of the membranes is obtained. The thickness of the polybutadiene coating is an important factor determining the ability of ions to pass across the membrane. Marked differences in the ionic resistance are observed as a function of the nature of the interlayer macrocyclic compound. For non-intercalated montmorillonite membranes, the ionic resistance is strongly reduced, whereas for some crown-ether intercalated materials such as 18-crown-6 and dibenzo 24-crown-8, iono-selective membranes are obtained. Concerning the nature of the electrolyte, cations exhibiting greater hydration energies show higher difficulties to pass through the membrane and, consequently, the ionic resistance increases. 相似文献
997.
A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc. 相似文献
998.
The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (ACDP) in the presence of n-octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first-order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six-fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k1/(s?1) = (31.8 ± 2.5) ? [(39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one O? O bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc. 相似文献
999.
We give some sufficient conditions for proper lower semicontinuous functions on metric spaces to have error bounds (with exponents).
For a proper convex function f on a normed space X the existence of a local error bound implies that of a global error bound. If in addition X is a Banach space, then error bounds can be characterized by the subdifferential of f. In a reflexive Banach space X, we further obtain several sufficient and necessary conditions for the existence of error bounds in terms of the lower Dini
derivative of f.
Received: April 27, 2001 / Accepted: November 6, 2001?Published online April 12, 2002 相似文献
1000.
We report the temperature dependence of electrical resistance (R) and thermopower (S) of clathrate Cs8Sn44 under high pressure up to 1.2 GPa. We observe a reversible gap widening, prominent relaxation effect of R, irreversible increase of |S| under high pressure. We also find that the power factor S2σ (σ: electrical conductivity) reaches a maximum at pressure of 0.3 GPa. Comparison of the experimental results with band structure calculations suggests that the intrinsic vacancy in the clathrate structure of Cs8Sn44 plays an important role in transport properties under high pressure. Measurements on Cs8Zn4Sn42, a clathrate which has defects other than vacancies, are compared with Cs8Sn44. The results indicate that replacing Sn by Zn has similar effect as the intrinsic vacancy on S. 相似文献