Liquid-phase noncatalytic butene oxidation with nitrous oxide

The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation energies and have the first orders with respect to the alkene and N₂O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation of terminal and internal alkenes C₂—C₈ with nitrous oxide were analyzed using the previously published data. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–933, April, 2005.     

High-temperature carboxidation of cyclopentene with nitrous oxide

It is demonstrated by the example of cyclopentene that the noncatalytic oxidation of alkenes with nitrous oxide to carbonyl compounds (carboxidation), which is known to occur in the liquid phase at 150–250°C, can also take place in the gas phase at higher temperatures (300–475°C). Like liquid-phase carboxidation, the gas-phase reaction likely proceeds via a dipolar 1,3-addition mechanism. However, 4-pentenal is formed along with cyclopentanone in the gas phase. The 4-pentenal selectivity increases from 2.5 to 23% as the reaction temperature is raised. High-temperature cyclopentene carboxidation can be carried out in a paraffin melt (bp ～ 400°C). Filling the reactor with paraffin accelerates the reaction and reduces its activation energy.     

Regularity of spike trains and harmony perception in a model of the auditory system

Spike train regularity of the noisy neural auditory system model under the influence of two sinusoidal signals with different frequencies is investigated. For the increasing ratio m/n of the input signal frequencies (m, n are natural numbers) the linear growth of the regularity is found at the fixed difference (m - n). It is shown that the spike train regularity in the model is high for harmonious chords of input tones and low for dissonant ones.     

Structure of the correlation dependence of nonlinear stochastic functionals

Radiophysics and Quantum Electronics -     

Diffusion in flashing periodic potentials

The one-dimensional overdamped Brownian motion in a symmetric periodic potential modulated by external time-reversible noise is analyzed. The calculation of the effective diffusion coefficient is reduced to the mean first passage time problem. We derive general equations to calculate the effective diffusion coefficient of Brownian particles moving in arbitrary supersymmetric potential modulated by: (i) an external white Gaussian noise and (ii) a Markovian dichotomous noise. For both cases the exact expressions for the effective diffusion coefficient are derived. We obtain acceleration of diffusion in comparison with the free diffusion case for fast fluctuating potentials with arbitrary profile and for sawtooth potential in case (ii). In this case the parameter region where this effect can be observed is given. We obtain also a finite net diffusion in the absence of thermal noise. For rectangular potential the diffusion slows down, for all parameters of noise and of potential, in comparison with the case when particles diffuse freely.     

Effective relaxation time of the impurity concentration in a medium with a slightly nonuniform diffusion coefficient

Based on the previously introduced integral criterion and a new approach to estimating the time characteristics of diffusion, the relaxation time of impurity concentration in a medium with a slightly nonuniform diffusion coefficient is determined. The diffusion coefficient profile that cuts the relaxation time is found.     

Isomerization of 1-Butene to 2-Butenes in the Presence of Acid-Base Catalysts

Russian Journal of Applied Chemistry - The possibility of reaching the equilibrium in structural isomerization of 1-butene on acid-base catalysts in the temperature interval 20–100°C was...