Nonequilibrium vibrational populations of diatomic species in electrical discharges: Effects on the dissociation rates

Dissociation rates of N₂ in N₂-H₂ mixtures and of H₂ in Ar-H₂ mixtures have been calculated for conditions typical of gas discharges. The results have been obtained by solving a system of master equations including V-V (vibration-vibration), V-T (vibration-translation) and e-V (electron-vibration) energy exchanges. The results show that these rates are much smaller than the corresponding ones for pure gases, as a consequence of the increased importance of V-T processes. A simplified model, which takes into account the main features of the distribution of vibrational levels in an electrical discharge, has been built up to rationalize the present results as well as those derived in our previous work.     

Quantum-chemical investigation of the protonated forms of 2-(2-furyl)pyrrole

The electron and conformational structures, as well as the internal rotation, of 2-(2-furyl)pyrrole and its -protonated forms were studied by the MNDO method with complete optimization of the geometry. In conformity with the experiments (PMR), the two delocalized cations with a cis orientation of the heteroatoms that are formed as a result of protonation of the pyrrole or furan ring have the greatest and virtually equal stabilities (H=738.7 and 740.6 kJ/mole).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 746–753, June, 1991.     

Fluoroaliphatic esters of fluorosulfonic acid. 4. Reactions of α-fluorosulfatoperfluoro ketones with nucleophilic reagents

-Fluorosulfatoperfluoroethyl isopropyl ketone I and fluorosulfatopentafluoroacetone II react with alkali metal chlorides and bromides to form the corresponding -haloperfluoro ketones as a result of direct nucleophilic substitution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2066–2069, September, 1990.     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol.     

Discussion on the method for the measurement of the flexural modulus of coupled materials and reasons of the shifts of theQ −1 maxima caused by coupling

Summary When measuringQ ^–1 and the flexural resonance frequency of bars clamped at one end, constituted by a viscoelastic polymeric material glued to a rigid support of modulusE ₁, it is possible to calculate the componentsE ₂ andE ₂ of the complex elastic modulus of the polymeric material examined. In this work the minimum (critical) value of the ratioa=E ₂ /E ₁=a _c and the values of the ratioQ ₂ ^–1/Q ^–1=F ₁ are evaluated beyond which no exact calculation ofE ₂ and ofQ ₂ ^–1 is possible.Within the confidence limits of the linear viscoelasticity theory, these values depend on the accuracy of measurement of both frequency and resonance curve, as well as on the instrument employed, on the operating temperature and on the ratio between the thicknesses of the two coupled materials.In order to keep outside the critical conditions, the most convenient method involves the use of measurements of coupled test-pieces having different ratiosz between their thicknesses and of supports having different modulusE ₁, depending on the field of temperature of the analysis ofE ₂ and tg ₂ concerning and E.P.R. elastomer and a vulcanized cis-1,4 polyisoprene in very wide ranges of temperature comprising the glass transition. Moreover, it is demonstrated by analysis the shift on the temperature axis of the tg maximum of the composite test-piece with respect to the position of the tg maximum of the polymeric material alone.With 11 figures and 1 table