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51.
M.?Avramov Ivi?Email author J.?Popi? D.?Antonovi? 《Russian Journal of Electrochemistry》2005,41(3):270-274
Electrocatalytic properties of oxides formed at gold, platinum, and stainless steel electrodes in the malic acid electrooxidation in 0.1 M Na2SO4 are studied. Gas chromatographic analysis of the electrolyte after holding the potential at 1.0 V for 8 h shows that on platinum and gold electrodes 2 mmol of acetaldehyde are produced and on stainless steel, 45 mmol. The acetaldehyde yield is the highest on stainless steel.From Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 304–309.Original English Text Copyright © 2005 by Avramov Ivi, Popi, Antonovi.This article was submitted by the authors in English. 相似文献
52.
V. P. Lebedev V. V. Chironov A. N. Kizin I. F. Falyahov I. Sh. Saifullin O. R. Klyuchnikov Yu. D. Orlov Yu. A. Lebedev 《Russian Chemical Bulletin》1995,44(4):639-641
The enthalpies of combustion of some pyridine derivatives in the solid state have been measured by precision bomb calorimetry, and their enthalpies of formation have been calculated. The enthalpies of sublimation of these compounds have been determined from the experimental temperature dependences of saturated vapor pressure using the Clausius-Clapeyron equation. The enthalpies of combustion, formation, and sublimation are the following (kJ mol–1): -3360.9±2.1, -0.5±2.1, and 79.1±1.3, respectively, for 4-methylpyridine 1-oxide; -2551.0±1.7, 11.7±1.7, and 89.1±2.5, respectively, for 4-nitropyridine 1-oxide;-2355.6±1.3, 102.1±1.3, and 106.3±2.9 for 2,4,6-trinitropyridine 1-oxide; and -2287.6±1.3, 34.3±1.3, and 101.7±2.9 for 2,4,6-trinitropyridine. The enthalpies of formation in the solid state and the enthalpies of sublimation of pyridine derivatives obtained together with the literature data allowed the energies of dissociation of the donor-acceptor N—O bonds in pyridine 1-oxides to be calculated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 660–662, April, 1995. 相似文献
53.
The use of H-point curve isolation (HPCIM) and H-point standard addition methods (HPSAM) for spectrophotometric studies of complex formation equilibria are proposed. One step complex formation, two successive stepwise and mononuclear complex formation systems, and competitive complexation systems are studied successfully by the proposed methods. HPCIM is used for extracting the spectrum of complex or sum of complex species and HPSAM is used for calculation of equilibrium concentrations of ligand for each sample. The outputs of these procedures are complete concentration profiles of equilibrium system, spectral profile of intermediate components, and good estimation of conditional formation constants. The reliability of the method is evaluated using model data. Spectrophotometric studies of murexide-calcium, dithizone-nickel, methyl thymol blue (MTB)-copper, and competition of murexide and sulfate ions for complexation with zinc, are used as experimental model systems with different complexation stoichiometries and spectral overlapping of involved components. 相似文献
54.
Clovis Peppe Paola de Azevedo Mello Rafael Pavão das Chagas 《Journal of organometallic chemistry》2006,691(11):2335-2339
The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles. 相似文献
55.
We study a nonlinear fourth order evolution equation arising in the context of sand ripple dynamics. We analyse the set of stationary solutions and travelling waves in order to recover the observed phenomenology such as different wavelengths ripples, travelling waves, coarsening and time scales. Moreover, we construct an approximate solution which describes the early stages of the dynamics and which suggests the existence of coarsening and of time scales with different dynamical behaviour. 相似文献
56.
Highly efficient kinetic resolution of racemic secondary alkyl diazoacetates in intramolecular carbon-hydrogen insertion reactions has been achieved using chiral dirhodium(ii) carboxamidates. Products formed from catalytic diazo decomposition of racemic 2-octyl diazoacetate and, separately, its (2R)- and (2S)-enantiomeric forms, as well as bothcis- andtrans-2-methylcyclohexyl diazoacetates, have been systematically evaluated. Enantioselectivities up to 99 %ee have been obtained for -lactone formation. -Lactone production has been observed and, although minor with cyclohexyl diazoacetates, is the major insertion pathway for diazo decomposition of 2-octyl diazoacetate.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1798–1803, September, 1995.Financial support for this research from the National Institutes of Health (GM 46503) and the National Science Foundation of the United States is gratefully acknowledged. We thank D. A. Pierson for her preparation of 2-methylcyclohexyl diazoacetates and preliminary studies of their diazo decomposition and A. Melekhov from the Higher College of Chemistry for his preparation and catalytic studies of rac-2-octyl diazoacetate. 相似文献
57.
Phase transitions and hysteresis in a cellular automata-based model of opinion formation 总被引:1,自引:0,他引:1
A particular case of a cellular automata-based model of two-state opinion formation in social groups with a strong leader is studied. We consider a 2D Euclidian geometry of social space and mutual interactions 1/r
n
. The model shows an interesting dynamics which can be analytically calculated. There are two stable states of the system: a cluster around the leader and unification. Unstable clusters may also appear. A variation in parameters such as the leader's strength or the social temperature can change the size of a cluster or, when they reach some critical values, make the system jump into another state. For a certain range of parameters the system exhibits bistability and hysteresis phenomena. We obtained explicit formulas for the cluster size, critical leader's strength, and critical social temperature. These analytical results are verified by computer simulations. 相似文献
58.
An electrostatic bond energy model is formulated to fit the enthalpies of formation and dipole moments of the alkanes and chloroalkanes. In this model, the charge distributions are calculated by an electrostatic approach similar to the "MSE" method, and the enthalpy of formation of a molecule is the sum of the bond energy terms plus the electrostatic energy of the interactions between the charges on all atoms. All parameters of this model are obtained by parameterization. The calculated dipole moments for 13 chloroalkanes and enthalpies of formation for 19 alkanes and non-geminal chloroalkanes agree with the determined values very well. To calculate the enthalpies of formation of geminal chloroalkanes, a correction mainly attributed to the van der Waals interactions in the geminal substituted group, about 24 kJ/mol per pair of geminal chlorine atoms, is introduced. 相似文献
59.
Min Hsien Liu 《中国化学会会志》2007,54(1):141-148
Density functional theory (DFT) calculations are made and least squares calibration performed for various halohydrocabons, which were 27 straight‐chain alkyl halides, 20 branch‐chain alkyl halides and 19 aromatic halides, to determine their enthalpies of formation (ΔHf). The mean absolute error (M. |A.E.|) in ΔHf across 66 molecular computations was only 7.8 kJ/mol (1.9 kcal/mol). Grouping the molecules by their structural characteristics improved M. |A.E.| of ΔHf by 0.2–2.2 kJ/mol over that obtained using corresponding modified data for the same 66 unclassified molecules. 相似文献
60.
A. K. Galwey 《Journal of Thermal Analysis and Calorimetry》2005,82(2):423-437
Summary A representational model, proposed to account for the physical changes that accompany the melting of alkali halides, was described
in Part 1 [1]. The liquid is portrayed as undergoing continual dynamic structural reorganization of its constituent ions between
individual small domains, zones of various regular, crystal-type arrays. These alternative arrangements are stabilized by
the enthalpy of melting, which, in liquids, relaxes the restriction for solids that only the single, most stable, crystal
structure can be present. The dynamic character of the melt accounts for its fluid character and the loss of long-range order
[1, 2]. This model is extended here to consider the phase diagrams of binary, common ion, alkali halide mixtures comprehensively
reviewed in [3]. Factors determining whether each of these yields a eutectic, or a solid solution, on cooling are discussed
and several trends in the 70-phase diagrams are identified. Eutectic formation, involving maintenance of the liquid state
below the melting points of the pure components, is ascribed to the participation, in an extended dynamic equilibrium, of
additional domains having the regular structures characteristic of double salts. The known crystalline double binary halides
[3], Li/Cs or Rb/F, Cl, Br or I, melt at temperatures well below those of the simpler pure component salts. It is concluded
that the set/liq model for melting, proposed in [1, 2], accounts for some important properties of the phase diagrams presented
in [3]. 相似文献