Calculation of activation volumes of thermal conversions of trimethylsilyl(cumyl) peroxide by the spline approximation method

The overall rate constants k_s of thermal conversions of trimethylsilyl(cumyl) peroxide (TMSCP) at pressures P up to 10 kbar are separated into components taking into account the ratios of the corresponding products: the rate constants of radical decomposition k_d and the rate constant of rearrangement k _r. Spline approximation of experimental dependences of lnk on P is used to determine the continuous dependence of the activation volume V^# on P in the solvents cyclohexane, anisole, toluene, n-nonane, isopropylbenzene, and tert-butylbenzene. The dependences of V_s^#, V_d^#, V_r^# on P are synchronous and nonordinary, and their nature significantly depends on the choice of a solvent. Spline approximation of experimental dependences of the TMSCP concentrations on the reaction time in isopropylbenzene at various P is used to find differential constants k_s , which generally increase with the reaction time, especially in the pressure interval 5–10 kbar.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 836–841.Original Russian Text Copyright © 2004 by Zhulin, Rudakov, Antonovskii.     

Representations of the exceptional lie superalgebraE(3, 6) I: Degeneracy conditions

Recently one of the authors obtained a classification of simple infinite dimensional Lie superalgebras of vector fields which extends the well known classification of E. Cartan in the Lie algebra case. The list consists of many series defined by simple equations, and of several exceptional superalgebras, among themE(3, 6).In the article we study irreducible representations of the exceptional Lie superalgebraE(3, 6). This superalgebra hass(3)×s(2)×g(1) as the zero degree component of the consistent -grading which leads us to believe that its representation theory has potential for physical applications.Supported in part by NSF grant DMS-9970007.     

Adsorption and kinetics of the oxidation of ethylene on PdCl2/SiO2

A new variant of the kinetic distributive method was used to study the kinetics of the oxidation of ethylene by PdCl₂ complexes supported on silica gel taking account of the equilibrium distribution of ethylene between the gas phase, silica gel, and metal complex reaction sites. Mono-, bi-, and polynuclear palladium(II) species are found to participate in the reaction. The Pd^II activity increases with increasing amount of nuclei in the species. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg ul., Donetsk 83114, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 36, No. 4, pp. 243–246, July–August, 2000.     

Thermocapillary instability of a deformable liquid film

The instability of a plane liquid film with a uniform transverse temperature gradient under conditions of weightlessness is considered. The surface tension is assumed to depend linearly on the temperature. On the basis of an exact solution of the neutral perturbation problem for a layer with deformable boundaries, the instability domains, the dispersion curves, and the shape of the perturbations are determined. It is shown that on the interval of low Prandtl numbers both thermocapillary waves with predominantly longitudinal flow and capillary waves, supported by the thermocapillary effect, with intense transverse liquid flow can develop on the film.Perm'. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 5, pp. 30–36, September–October, 1996.     

Study of the interaction of hydrogen with palladium-containing catalysts of methane oxidation

The reaction of palladium-containing catalysts PdCl₂/SiO₂ [ratio of the components 0.3:100 (molar)] with H₂ (300°C) after methane oxidation leads to the formation of RH: methane, ethane, propane, n-butane, and isobutane. The sources of RH are PdC_x — products of incomplete oxidation of CH₄ — as well as organic impurities in silica gel. Additions of NaCl (NaCl:SiO₂ = 7:100) triple the yield of RH. Catalysts with additions of H₂SO₄ (H₂SO₄:SiO₂ = 40.100) are not hydrogenated to RH.L. M. Litvinenko Institute of Physico-Organic Chemistry and Coal Tar Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg Street, Donetsk 340114, Ukraine. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 3, pp. 177–181, May–June, 1996. Original article submitted July 20, 1995.     

Electrochemical thiocyanation of dodecahydro-7,8-dicarba-<Emphasis Type="Italic">nido</Emphasis>-undecaborate and 7,8-dimethyldecahydro-7,8-dicarba-<Emphasis Type="Italic">nido</Emphasis>-undecaborate monoanions

Electrochemical thiocyanation of the dodecahydro-7,8-dicarba-nido-undecaborate and 7,8-dimethyldecahydro-7,8-dicarba-nido-undecaborate monoanions afforded thiocyanate derivatives of these compounds, which were isolated as alkylammonium salts. The structures of the synthesized compounds were determined by the data from IR, ¹H and ¹¹B NMR, and ¹¹B-¹¹B NMR COSY spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1553–1556, July, 2005.     

Qualitative Identification of Milk Fat from Chromatographic Data

The data on the amount of fatty acids in milk, animal, vegetable, and mixed fats were obtained by capillary gas–liquid chromatography. Statistical data on the concentrations of myristic, palmitic, stearic, oleic, linoleic, and linolenic acids in milk fat were considered as criteria of its natural origin. Concepts were formulated for the detection of a multicomponent adulterating additive of variable composition in a product containing variable amounts of the same components. A graphical interpretation of the results of the analysis was proposed based on the identification zone.