The oxonium theory in the light of an optical study of the hydrogen bond in some monovinyl ethers of glycols and polyglycols

Summary An optical investigation of some monovinyl ethers of glycols and polyglycols has indicated the presence of intermolecular hydrogen bonds in the liquid state, and this is confirmed by data derived from other phycicochemical investigations. The presence of an intermolecular hydrogen bond explains the anomalous valency of the oxygen atom of the investigated class of ethers (Its oxonium character), and also peculiarities of the properties of these ethers.     

Tautomerism and dual reactivity

Summary Dual reactivity in substances is due to the tautomerism of molecules in accordance with Scheme I or (particularly in cases previously assigned to the field of pseudomerism) to the tautomerism of intermediate ions and radicals in accordance with Scheme III in, in which the tautomeric forms (molecules, ions, radicals) have separate existences. These particles, which exist separately in a state of equilibrium reversible isomerization, can give two series of derivatives under the appropriate conditions, and this is confirmed by physical investigation of the matter [12].This paper is published as a polemic contribution.     

Optical investigation of the conformations of cyclopentanone and α-chlorocyclopentanone

Summary Cyclopentanone exists in two conformations — with a quasi-axial (V) and a quasi-equatorial (VI) position for the carbonyl group. -Chlorocyclopentanone exists in four conformations: (VIDtrans-la'-2a(VIII) trans-le'2e, (DC) cis-la'2a=(X) cis-1a'2e.     

Modified Ceria-Zirconia Fluorite-Like Catalysts for the Combustion of Methane

For dispersed ceria-zirconia-based solid solutions prepared via the polymerized complex method and annealed at 700℃, effects of bulk doping by Ca, Mn, Co, Bi or Nb cations and surface modification by Mn and Pt on their structural features, surface/bulk oxygen reactivity and catalytic activity in methane combustion are considered. With up to 20 mol% doping, a structural type of homogeneous solid solutions of anion-deficient fluorite with disordered anion vacancies is formed. Doping by transition metal cations or Pt increases the mobility and reactivity of the surface/bulk oxygen. A broad variation in specific rates of methane combustion for the studied systems was observed, suggesting structural sensitivity of this reaction. In general, there is no universal relationship between the oxygen mobility, the reactivity and the catalytic activity in methane combustion, which is explained by the factor of specific methane activation on surface active sites. For the Pt-promoted samples, Pt efficiency in methane activation depends on the Pt-support interaction, and the most favorable ones being mixed Pt/MnOx and Pt/NbOx clusters on the surface of the supports that exhibit high lattice oxygen mobilities.     

Raman-spectrum investigation of the conformations of cis-and trans-1,3-dimethylcyclohexanols

Summary When configurations are named with respect to the actually largest substituents, the preferred conformation for the compound (I) in the liquid phase is trans-1e3a, and for compound (II) in the liquid phase cis-1e3e with equatorial hydrogen-bonded hydroxyls; when this nomenclature, based on the actually largest substituents is used, the Auwers-Sktta rule is not reversed for the compounds (I) and (II) in the liquid state.     

Raman spectrum of 1,5-hexadien-3-yne

Summary In the liquid phase, 1,5-hexadien-3-yne apparently exists as a mixture of two isomers, namely cis (I) and trans (II) forms with (I) predominating.     

Raman-spectrum investigation of some acetylenic alcohols and their acetic esters

Summary The formation of the acetic esters of tri- and di-bromo ketols by the action of HOBr on the acetic esters of secondary and tertiary acetylenic alcohols is due to the particularly strongly protonized (acidic) hydrogen atom of the methylidyne group=C-H, which results from profound frequency modulation of the vibrations of the latter by the low-frequency intermolecular vibrations at the hydrogen bonds.