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951.
V. P. Feshin M. Yu. Kon'shin A. V. Radushev E. V. Feshina V. Yu. Gusev A. E. Lesnov V. I. Karmanov 《Russian Chemical Bulletin》1996,45(11):2505-2508
The basicity of hydrazides of the highest aliphatic carboxylic acids RC(O)NHNH2 (R = CnH2n+1,n = 5-12) has been studied by potentiometric titration, and IR and1H NMR spectroscopy.Ab initio Hartree-Fork calculations using the 6–31G* basis set with full optimization of geometry were carried out on the simplest acy1hydrazines and their possible protonated forms. Based on these calculations, and the 1R and1H NMR spectra, the tautomerism of alkylhydrazides and the structures of their protonated forms are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2645–2649, November, 1996. 相似文献
952.
C. Christov S. Petrenko C. Balarew V. Valyashko 《Monatshefte für Chemie / Chemical Monthly》1994,125(12):1371-1382
Summary The standard method ofPitzer for predicting the solubility isotherms of systems in which solid phases with a constant composition crystallize is applied to cases when mixed crystals are formed. The four-component carnallite type systems RbCl-CsCl-MgCl2-H2O, RbCl-KCl-MgCl2-H2O, and RbCl-RbBr-MgCl2-MgBr2-H2O and the corresponding subsystems are thermodynamically simulated at 25°C. It is established that the solubility diagrams consist of crystallization regions of the simple saltsMX,MX, MgX
2·6H2O, and MgX2·6H2O and of the corresponding carnallite type double salts with the composition 1:1:6. A method of calculation of the integralGibbs energy of mixingG
mix(s) of crystals formed in water-salt systems has been proposed. The results on the systems RbCl-KCl-H2O, RbCl-RbBr-H2O, and MgCl2-MgBr2-H2O are compared with experimental data from the literature and with values calculated using various models.
Thermodynamische Simulation von Vierkomponentensystemen des Carnallit-Types
Zusammenfassung DiePitzer-Methode zur Voraussage der Löslichkeitsisothermen in Mehrstoffsystemen, in welchen feste Phasen mit konstanter Zusammensetzung auskristallisieren, wurde auch für Fälle angewendet, bei denen sich Mischkristalle bilden. Die Vierstoffsysteme RbCl-CsCl-MgCl2-H2O, RbCl-KCl-MgCl2-H2O und RbCl-RbBr-MgCl2-MgBr2-H2O, aus welchen Carnallit-Typ-Mischkristalle auskristallisieren, und die dazugehörigen Dreistoff-Randsysteme wurden bei 25°C simuliert. Man stellt fest, daß die Löslichkeitsdiagramme sowohl Kristallisationsbereiche der einfachen SalzeMX,M'X, MgX 2·6H2O und MgX 2·6H2O als auch der entsprechenden carnallitartigen Doppelsalze mit der Zuzammensetzung 1:1:6 umfassen. Eine Methode zur Berechnung derGibbs-EnergieG mix(s) für die in Wasser-Salz-Systemen gebildeten Mischkristalle wird vorgeschlagen. Die für die Systeme RbCl-KCl-H2O, RbCl-RbBr-H2O und MgCl2-MgBr2-H2O erhaltenen Ergebnisse werden mit experimentellen Literaturdaten und Resultaten von Berechnungen aufgrund verschiedener Modelle verglichen.相似文献
953.
Improved separations of the isomers of olefinic aliphatic insect pheromones were obtained on cholesteryl cinnamate glass capillary columns by operating in the supercooled temperature range of the liquid crystal. Capillary columns were prepared with varying film thickness of the stationary phase; choice of the correct film thickness ensured optimum retention for a wide range of compounds within the most effective temperature range of the liquid crystal. The deactivation procedures described made the liquid crystal columns suitable for separation of the geometric isomers of polar and nonpolar compounds. 相似文献
954.
Enthalpies of solution of sodium octanoate in water, 1-propanol and aqueous mixtures of 1-propanol, 1-butanol, 1-pentanol and 1-hexanol, and of the alcohols in aqueous solutions of sodium octanoate at various concentrations were determined calorimetrically at 35 °C. MostH(soln) values are exothermic and strongly dependent on the solute concentration. The main energetic factor governing the process of dissolution of the surfactant is associated with changes in the water structure caused by the presence of alcohol. That governing the process of the alcohol dissolution in surfactant solutions is due to the effect alcohols have on the CMC of the octanoate. There is no indication of the alcohol being either solubilized in the interior of the aqueous micelle, or becoming part of the micellar film.The solubility at 35 °C of sodium octanoate in water, 1-propanol and their mixtures has also been determined. 相似文献
955.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether. 相似文献
956.
We optimized the hot water extraction of polysaccharides from the root of Henry wood betony (RHWPs) using a uniform test and explored their anti-tumor activities in vitro and in vivo. The optimal extraction conditions were as follows: 40 min extraction time, liquid/solid ratio 30 mL/g, 100 min soaking time, two extraction cycles, 100% ethanol concentration, and extraction temperature of 80 °C. The molecular weight distribution of RHWPs with MWs was 228,600 g/mol and 5001 g/mol. The IR spectrum further indicated that RHWPs are acidic polysaccharides containing pyranose and furan rings. The main monosaccharides found in RHWPs were mannose, ribose, l-rhamnose monohydrate, glucuronic acid, galacturonic acid, glucose, galactose, xylose, arabinose, and fucose. RHWPs inhibited the proliferation of S180 tumor cells and induced apoptosis in vitro. Oral administration of RHWPs to tumor-bearing mice significantly inhibited the growth of the S180 xenografts, accelerated apoptosis in tumor cells, and expanded the necrotic regions. Furthermore, RHWPs also markedly increased the levels of TNF-α, IFN-γ, and IL-2 in the sera of tumor-bearing mice, and activated immune cells such as lymphocytes, NK cells, and macrophages, thereby inducing tumor cell apoptosis. Taken together, RHWPs are a promising anti-tumor agent that ought to be explored further. 相似文献
957.
氯化钪-氯化钠-氯化钾熔盐制备新工艺研究 总被引:3,自引:1,他引:3
研究了以Sc2O3为原料,盐酸回流溶解后与NaCl,KCl,NH4Cl溶液混合,经蒸发浓缩、结晶、真空预脱水,再在氩气保护下分段升温脱水、升华除去过量NI-hCl后制备ScCl3-NaCl-KCl熔盐的新工艺。研究表明,添加NH4Cl后加热脱水时,NH4Cl分解产生的HCl气体能抑制ScCl3水合物加热过程中的水解,溶解产生的水不溶性钪,从而有效地防止了Sc2O3等水不溶化合物的生成。制备的ScCl3-NaCl-KCl熔盐脱水完全、水不溶性钪含量很低,能满足熔盐金属热还原法制备金属钪及铝钪中间合金对熔盐原料的要求。 相似文献
958.
用定量体积排除色谱方法研究了过渡金属Fe(Ⅲ)、Co(Ⅲ)、Cu(Ⅱ)、Ni(Ⅱ)的乙酰丙酮螯合物在四氢呋喃溶液中的加合和缔合行为。在溶液中乙酰丙酮钴(Ⅲ)以单个螯合物分子的形式存在,乙酰丙酮铜(Ⅱ)和乙酰丙酮铁(Ⅲ)与溶剂加合生成加合物,乙酰丙酮铁(Ⅲ)除加合物外还存在缔合度为2-10的多分散缔合物,乙酰丙酮镍(Ⅱ)水合物在四氢呋喃中产生了加合交换作用,同时存在缔合度为6左右的缔合物。色谱数据给出了螯合物、加合物及缔合物 相似文献
959.
Comparability of analytical results obtained in proficiency testing based on a metrological approach
Ilya Kuselman 《Accreditation and quality assurance》2006,10(9):466-470
A “yes–no” type of criterion is proposed for the assessment of comparability of proficiency testing (PT) results when the PT scheme is based on a metrological approach, i.e. on the use of a reference material as the test sample, etc. The criterion tests a null hypothesis concerning the insignificance of a bias of the mean of the results from a traceable value certified in the reference material used for the PT. Reliability of such assessment is determined by the probabilities of not rejecting the null hypothesis when it is true, and rejecting it when it is false (the alternative hypothesis is true). It is shown that a number of chemical, metrological and statistical reasons should be taken into account for careful formulation of the hypotheses, enabling the avoidance of an erroneous assessment of the comparability. The criterion can be helpful for PT providers and laboratory accreditation bodies in analysis of PT results. 相似文献
960.
近年来,实验发现钛酸铅基材料具有负热膨胀性,且其热膨胀程度会受到掺杂元素的影响. 目前所研究的A位掺杂体系中,仅Cd原子掺杂能使钛酸铅负热膨胀性增强. 所以研究A位掺杂钛酸铅,比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同,有助于深刻理解钛酸铅负热膨胀的本质. 本文利用第一性原理,分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数,计算了它们的态密度和电荷密度. 结果表明Cd―O键的共价性强于Pb―O键,而Ba―O键和Sr―O键几乎呈离子性,Ba/Sr对Pb的替代削弱了化合物的共价性,降低了自发极化强度. 与实验测量的热膨胀系数对比可以发现,A位原子与氧原子之间的共价性增强,化合物负热膨胀程度升高;若A位原子与氧原子之间的共价性削弱,负热膨胀程度降低. 可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性. 相似文献