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71.
On Calcium Bromated and Iodates – Crystal Structure, X-Ray, IR and Raman Spectroscopical and Thermoanalytical Investigations The phase relationships (and both decomposition and disproportionation)of bromates and iodates of alkaline earth metals are studied by means of thermal analyses (DTA, DSC, TG) and (high-temperature) X-Ray, IR-, and (high-temperature) Raman spectroscopic measurements. The following compounds have been established: Ca(IO3)2 · 6 H2O oF 216, the isotypic Ca(BrO3)2 · H2O and Ca(IO3)2 · H2O mP 48, Ca(IO3)2 I (Lautarit) mP 36, Ca(IO3)2 II and Ca(BrO3)2. The Crystal structure of Ca(IO3)2 · H2O (brüggenite) (space group P21/c, Z = 4) has been determined by single crystal X-ray diffraction (MoKα). The final R value for 3888 reflections with Io > 3σ1 is 0.0487. The structures of bromates and iodates of alkaline earth metals known so far are discussed with respect to the energetic (mode frequencies) and geometric (bond lengths) distortion of the XO3–ions as well as the strengths of H-bonds present in the respective hydrates. 相似文献
72.
The structures of the stable conformers of N-methyjpropionamide and N-methyliso-butyroamide in CCl4, solution were determined by a combination of IR spectroscopy and NMR spectroscopy with lanthanide shift reagents. N-methyl-propionamide was found to exist in the form of two rotational isomers, 1 and 2, with the ethyl group twisted out of the plane of the amide bond by the angles Ψ = 140 and 20°, respectively. For these two conformers, the enthalpy difference is ΔH = 2.13 ± 0.08 kcal mole?1 and the entropy difference ΔS = 7.81 ± 0.55 cal mole?1 grad?1. N-methylisobutyroamide exists in a single form, with the two C-methyl group positions very close to those found in the two isomers of N-methylpropionamide. 相似文献
73.
The vaterite—calcite transition above 630 K has been studied by isothermal and non-isothermal differential scanning calorimetry. Vaterite samples prepared under different conditions were investigated. The transition temperature is strongly dependent on the sample preparation. The observed transition enthalpy Htr is nearly equal for different samples and experimental conditions. From 28 measurements a value of Htr–(3.12±0.11) kJ mol–1 was obtained. The activation energy for the polymorphic transition was calculated from the Arrhenius plot and by use of isoconversional methods, as a function of the degree of conversion. The influence of the kinetic model distortion and experimental uncertainties on the obtained data was discussed. The actual value of the activation energy was assessed at Ea=(250±10) kJ mol–1 for nearly all examined samples. Functions, corresponded to the model mechanism of nuclei formation and growth, provide the unambiguous consideration of the transition kinetic for the investigated vaterite samples. Differences in the dynamic behaviour of several samples at the transition are established.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
74.
MM. J. Duflos D. Letouz G. Queguiner P. Pastour 《Journal of heterocyclic chemistry》1973,10(6):1083-1084
This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine. 相似文献
75.
Attempts to prepare phosphate granates were without success. However, three arsenate granates of the type {NaCa2}[M](As3)O12 with MII ? Mg, Co, Ni have been prepared by solid state reaction and their lattice constants determined. All these arsenates are characterised by a thermal transformation into a high-temperature form, proceeding monotropically for the Mg compound, and reversibly for the Ni and Co compound. 相似文献
76.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
77.
Kwac and Cho [J. Chem. Phys. 119, 2247 (2003)] have recently developed a combined electronic structure/molecular dynamics approach to vibrational spectroscopy in liquids. The method involves fitting ab initio vibrational frequencies for a solute in a cluster of solvent molecules to a linear combination of the electrostatic potentials on the solute atoms due to the charges on the solvent molecules. These authors applied their method to the N-methylacetamide-D/D(2)O system. We (S. A. Corcelli, C. P. Lawrence, and J. L. Skinner, [J. Chem. Phys. 120, 8107 (2004)]) have recently explored a closely related method, where instead of the electrostatic potential, the solute vibrational frequencies are fit to the components of the electric fields on the solute atoms due to the solvent molecules. We applied our method to the HOD/D(2)O and HOD/H(2)O systems. In order to make a direct comparison of these two approaches, in this paper we apply their method to the water system, and our method to the N-methylacetamide system. For the water system we find that the electric field method is superior to the potential approach, as judged by comparison with experiments for the absorption line shape. For the N-methylacetamide system the two methods are comparable. 相似文献
78.
Phosphine or phosphonium iodide react with boron triiodide in CS2 or benzene to form the adduct H3P–BI3. The water-sensitive white solid is thermally stable up to ~150°C. Its IR and NMR spectrum are recorded. 相似文献
79.
Contributions to the Chemical Transport of Metal Oxides. V. Transport of Ternary and Quaternary Mixed Ferrites by their Chlorides The transport by means of HCl as transporting gas in a closed system in the case of the ternary mixed ferrites (Ni0,8Fe2,2O4, Mn0,75Fe2,25O4, Mn1,286Fe1,714O4) and the quaternary mixed ferrites (Mg0,5Mn0,5Fe2O4, Mg0,75Mn0,536Fe1,714O4, Mg0,281Mn0,469Fe2,25O4, Mn0,5Zn0,5Fe2O4, Mn0,5Zn0,45Fe2,05O4, Ni0,5Zn0,5Fe2O4) between T2 = 1100?1000°C and T1 = 1000?800°C was investigated. Transported crystals were characterized by chemical analysis and the saturation magnetization, the transport rate has been checked. In the case of Mn0,5Zn0,45Fe2,05O4 two phases were transported. By discussing the phase diagram an explanation is given. 相似文献
80.
On the Reaction of Germanium with Germanium Tetrachloride and on the Existence of the Oxidechlorides GeOCl2 and GeOCl6 at the Equilibrium The above equilibrium was measured in a Gauge-manometer and the enthalpy of formation and the entropy for GeCl2,g were derived from these results. From total pressure measurements and transport experiments of GeO2 with GeCl4 follows, that the oxidechlorides Ge2OCl6 and GeOCl2 are not present in measurable concentrations, that means the enthalpy of formation of GeOCl2 must be higher than ?327 kJ · mol?1. 相似文献