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31.
The preparation of η-C3H5V(CO)5 from allyl chloride and sodium hexacarbonylvanadate (–I) is reported. Composition, IR and NMR spectra are in accordance with a π-bonded C3H5-moiety; the preparation has been extended to give complexes with substituted allyl groups. Furthermore (1-3-η-2-butenyl)pentacarbonylvanadium can be obtained by the addition of butadiene to HV (CO)6. 相似文献
32.
The phase diagram for the binary system K2CrO4CaCrO4 has been determined for CaCrO4 concentrations up to 60 mole%, using the techniques of differential thermal analysis, X-ray diffraction, and drop calorimetry. Essential features of the phase diagram are: the solid-solid phase transition for pure K2CrO4 at 670°C, β-K2CrO4 ? α-K2CrO4; a eutectoid reaction at 14 mole% CaCrO4 and 548°C, β-K2CrO4 ? α-K2CrO4 + K2CrO4 · CaCrO4; a peritectoid event at 50 mole% CaCrO4 and 640°C, β-K2CrO4 + CaCrO4 ? K2CrO4 · CaCrO4; and a eutectic reaction at 51 mole% CaCrO4 and 678°C, L ? β-K2CrO4 + CaCrO4. X-ray diffraction studies lead to the determination of the unit cell dimensions for the K2CrO4 · CaCrO4 double salt, a C-centered monoclinic form with a0 = 7.615(6) Å, b0 = 22.797(15) Å, c0 = 9.777(9) Å, β = 115.45(5)°. 相似文献
33.
The growth rate of isotactic polypropylene is deduced from microscopic observations during isothermal crystallizations. A change in the growth regime is observed at 138 C and interpreted as a Regime III Regime II transition, according to Hoffman's kinetic theory of polymer crystallization. A Regime II Regime I transition is also theoretically predicted at 155 C, i. e. at a temperature outside the investigated temperature range. The Regime III Regime II transition is related to the positive to negative change in the spherulite birefringence, which is generally attributed to a change in the organization of crystalline lamellae: quadritic arrays of intercrossing lamellae atT
c < 138 C (Regime III) and preferentially radiating lamellae atT
c > 138 C (Regime II). It is suggested that such a morphological change could be interpreted using the concept of non-adjacent re-entry introduced in Hoffman's kinetic theory. This interpretation could also explain the interspherulitic ruptures observed in negative spherulites. 相似文献
34.
The crystal structure of a second high-pressure copper vanadate phase, CuVO3(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (Rw = 0.051). The space group is rhombohedral, , with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [aR = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu+V5+O3 is proposed. This represents a unique example of Cu+ in an octahedral environment. 相似文献
35.
The equilibrium of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied. Biologically produced sulfur was obtained from a bioreactor of a hydrogen sulfide removal process in which the dominating organism is Thiobacillus sp. W5. Detailed knowledge of this reaction is essential to understand its effect on the process. The results were compared with the equilibrium of the reaction of sulfide with ‘inorganic’ elemental sulfur. The equilibrium between dissolved sodium sulfide and biologically produced sulfur particles can be described by an equilibrium constant, Kx, which consists of a weighted sum of constants for polysulfide ions of different chain length, rather than a true single equilibrium constant. For biologically produced sulfur pKx = 9.10 ± 0.08 (21 °C) and 9.17 ± 0.09 (35 °C) with an average polysulfide chain length x = 4.91 ± 0.32 (21 °C) and 4.59 ± 0.31 (35 °C). The pKx value for biologically produced sulfur is significantly higher than for reaction of dissolved sodium sulfide with inorganic sulfur (pKx = 8.82; 21 °C). This difference is probably caused by the negatively charged polymeric organic layer, which is present on biologically produced sulfur but absent with “inorganic” sulfur. Specific binding of polysulfide ions to the organic layer results in a higher polysulfide concentration at the reaction site compared to the bulk concentration. This results in an apparent decrease of the measured equilibrium constant, Kx. 相似文献
36.
James Y. Becker Larry L. Miller Frank R. Stermitz 《Journal of Electroanalytical Chemistry》1976,68(2):181-191
The electrochemical oxidation of the alkaloid laudanosine (Ia) to O-methylflavinantine (II) has been studied in acetonitrile solvent. Using cyclic voltammetry, rotating disc voltammetry and preparative electrolyses on several alkaloids, simple aliphatic amines and aromatic compounds, some aspects of the mechanism of this coupling reaction are elucidated. The first anodic wave for laudanosine at platinum has Ep=0.55 V vs. Ag/Ag+. The electrode rapidly becomes partially passivated at potentials above 0.5 V. This is due to a film which “dissolves” below 0.5 V, at a rate independent of the potential. It is shown that the reaction (Ia)→(II) proceeds at 0.5 V by initial oxidation of the amine moiety. If acids such as sodium bicarbonate are added to the anolyte the amine is protonated causing the first wave to disappear. Oxidation at 1.1 V under these acidic conditions produces the same product, but more rapidly and in significantly higher yield because electrode filming and side reactions resulting from the amine oxidation are abrogated. 相似文献
37.
C. Mioskowski A. Solladie-Cavallo G. Solladie 《Journal of organometallic chemistry》1978,149(3):C63-C65
Attachment of a Cr(CO)3 moiety to one of the aromatic rings in rigid diaryl ketones of very low prochirality followed by addition of a chiral and optically pure reagent leads to satisfactory asymmetric induction ~40%. Asymmetric induction is smaller in the case of acyclic systems. 相似文献
38.
The number of products and the H2/CH4 ratio obtained from the flow pyrolyses of (CH3)3GeH and (CH3)3SiH were very different. The (CH3)3GeH decomposition is consistent with the following mechanism:
The pyrolysis of (CH3)3SiH was found to be much more complex, presumably due to the formation of silicon-carbon double bonded intermediates and the (CH3)2Si(H)CH2 radical. We also present data which supports the presence of a H atom chain sequence during this pyrolysis. 相似文献
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39.
The degradation of acenaphthylene, acenaphthene, 2-methylnaphthalene, 2-methylindene, 3-methylindene and indene in water solutions was studied. These compounds at the 25-150 mug/l. level were almost totally degraded at ambient temperature within three days. The microbial population responsible for the degradation occurs naturally in ground-water taken from an aquifer in Ames, Iowa, which is contaminated with coal-tar products. These unidentified micro-organisms adapt readily to other waters when used as an inoculant for the degradation of aromatic compounds. The preservation of water to prevent such degradation was also investigated. Filtration through a 0.45-mum filter was found the most effective procedure for preserving the hydrocarbons in these waters. 相似文献
40.
The cis fused bicyclic sulfones 1a, 1c and 3a are lithiated in benzene with n-butyllithium under concomitant cis/trans isomerization of the ring fusion, involving intramolecular proton transfer. H/D exchange of the three α-hydrogens in protic solvents proceeds with retention of configuration. The lithiated sulfones are chlorinated with hexachloroethane (HCE) and show a strong preference for introduction of halogen at an equatorial α-position. 相似文献