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1.
Christel Laberty Jerzy Pielaszek Pierre Alphonse Abel Rousset 《Solid State Ionics》1998,110(3-4):293-302
Cation deficient spinels NixMn3−x□3δ/4O4+δ (0≤x≤1) have been prepared by thermal decomposition of mixed oxalates Nix/3Mn(3−x)/3(C2O4)·nH2O in air at 623 K. They have been characterised by temperature programmed reduction (TPR) under H2, the reaction being followed by gravimetric and powder X-ray diffraction measurements. It has been shown that TPR proceeds in several steps. The first steps correspond to the loss of nonstoichiometric oxygen leading to the formation of a stoichiometric oxide. During the following stages the manganese cations are reduced, causing the spinel structure to be destroyed, and the formation of solid solution of NiO in a cubic MnO. Subsequently, Ni2+ cations undergo a reduction to metallic nickel, and, finally, a mixture of nonstoichiometric MnO1−δ and metallic nickel is formed. These oxides contain a high level of vacancies which vary with the nickel content with a maximum of δ≈1 near x=0.6. This nonstoichiometry is ascribed both to the presence of Ni3+ and excess of Mn4+. 相似文献
2.
3.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
4.
The determination of the structure of the intermediate in the Bucherer-Bergs reaction (the transformation in aqueous solution of an aldehyde into the corresponding amino-acid via the hydantoin) showed that this reaction involved the formation of α-aminonitrile carbamate. The slow formation of the carbonic anhydride from the carbonate buffer limited the formation of that main intermediate which was in equilibrium with the α-aminonitrile. The variation of the stability of the carbamate vs pH is mainly determined by the concentration of CO2 dissolved in the mixture, but also by the equilibrated formation of products formed by the degradation of α-aminonitrile, i.e. the aminodinitrile and the cyanohydrin. 相似文献
5.
Neutron activation, applied to silver and copper based coinage, leads to a measure of the mean concentrations of major and 12 trace elements, even if their distribution is heterogeneous. The drawbacks of this activation method applied to such a matrix are shielding effects and high radioactivity of major elements. Both effects were avoided by accurately calculating the correction coefficients and by choosing the optimal working conditions. Analytical results obtained lead to a better knowledge of the chronology and origin of Armorican protohistorical coinage. 相似文献
6.
X. Devaux A. C. Vajpei A. Rousset A. Rocher M. Brieu Uma Kailash Chandra I. P. Saraswat 《Journal of Thermal Analysis and Calorimetry》1990,36(2):529-543
DSC measurements in air from 20 to 800° are reported on aged iron(III)-chromium(III) coprecipitated hydroxides (with Fe3+Cr3+ wt% ratios of 91, 73, 11, 37 and 19). A comparison of the DSC profiles of aged coprecipitates with the thermal behaviour of freshly precipitated and well characterized samples provided information on the modification occurring in the structure and reactivity of the coprecipitates on prolonged aging.
Dedicated to Professor Wahid U. Malik, Founder-President, Indian Council of Chemists, India, with profound regards and fond memories of his youthful enthusiasm and ceaseless and pioneering efforts towards the development of chemical education and research activities at the University of Roorkee, Roorkee, India, on the occasion of his 70th birthday.
Paper presented at the World Conference on Thermal Analysis, Capri (Italy), 1989.
We thank Professor J. Pescia, Dr.G. Ablart and N. Favillier of Laboratoire de Magnétisme et d'Electronique Quantique for their interest in this work. A. C. Vajpei expresses his gratefulness to C.N.R.S. and C.N.O.U.S., Paris, for financial support of this work. 相似文献
Zusammenfassung Es werden DSC-Messungen an gealterten kogefällten Eisen(III)Chrom(III)-hydroxiden (mit Fe3+Cr3+ Gewichtsanteilen von 91, 73, 11, 37 und 19) im Temperaturbereich von 20 bis 800° beschrieben. Ein Vergleich der DSC-Profile von gealterten Kofällungen mit dem thermischen Verhalten frisch gefällter und gut definierbarer Proben lieferte Informationen über die Veränderungen in Struktur und Reaktivität der Koniederschläge bei längerem Altern.
Dedicated to Professor Wahid U. Malik, Founder-President, Indian Council of Chemists, India, with profound regards and fond memories of his youthful enthusiasm and ceaseless and pioneering efforts towards the development of chemical education and research activities at the University of Roorkee, Roorkee, India, on the occasion of his 70th birthday.
Paper presented at the World Conference on Thermal Analysis, Capri (Italy), 1989.
We thank Professor J. Pescia, Dr.G. Ablart and N. Favillier of Laboratoire de Magnétisme et d'Electronique Quantique for their interest in this work. A. C. Vajpei expresses his gratefulness to C.N.R.S. and C.N.O.U.S., Paris, for financial support of this work. 相似文献
7.
8.
Triplet-singlet radiationless energy transfer between benzophenone and perylene in vitreous solution
We have measured at 77 K the “critical radius” R0 of the resonant intermolecular energy transfer from the triplet state of benzophenone to the singlet state of perylene, these two comporents being in vitreous solution. 相似文献
9.
In this paper, we present an experimental study of vibrational lattice modes in isotopic mixed crystals of benzophenone-h10 and -d10. Our results are discussed using theoretical and experimental data concerning other molecular isotopic mixed crystals. The spectra show two regions; in the first (ν < 100 cm?1) we did not observe an interaction between the various vibrational lattice bands; in the second region (ν > 100 cm?1), the interaction appears clearly. The 111.5 cm?1 and 73 cm?1 torsional modes of benzophenone-h10 have the same behaviour as the external modes throughout the whole concentration range (0–100% of benzophenone-d10). 相似文献
10.
Drouet C Alphonse P Fierro JL Rousset A 《Journal of colloid and interface science》2000,225(2):440-446
The equilibrium and kinetics of adsorption of NO and CO on nonstoichiometric nickel-copper manganites have been investigated through volumetric measurements. The adsorption isotherms were satisfactorily fitted to the Freundlich equation. The equilibrium coverages at 298 K were found to depend closely on the chemical composition of the oxide; thus, a decrease in the coverage beyond a maximum copper extent was observed. The adsorption isotherms of NO at various temperatures in the range from 298 to 473 K showed that the equilibrium coverage decreases with increasing temperature. This behavior enabled us to follow the logarithmic decrease of the heat of adsorption of NO on such surfaces. The adsorptions of NO and CO on surfaces preadsorbed with CO and NO, respectively, were also studied. These experiments showed the ability of NO to displace CO preadsorbed molecules whereas the contrary did not hold, suggesting the existence of common adsorption sites as well as some specific CO adsorption sites. Finally, some kinetic data are reported showing that the experimental adsorption results fit the Elovich equation (with t(0) approximately 0), although two distinct rate processes could be identified. Copyright 2000 Academic Press. 相似文献