Influence of the structure of the organoaluminum compound on the stereoregulating heterogeneity of catalytic systems based on TiCl4

The stereoregulating heterogeneity manifested in butadiene polymerization by active sites of the titanium catalytic system formed “separately” in combination with organoaluminum ligands was examined.     

Fluctuations of acoustic field in a granular medium

Results of an experimental study of sound propagation in a granular medium are presented. It is found that, in the case of excitation of a harmonic signal with a constant amplitude, the acoustic response of a single grain strongly varies in time. The dependence of the harmonic component amplitudes in the response spectrum on the level of signal excitation proves to be nonmonotonic and also strongly varies in time. The most intense fluctuations are observed in the subharmonic component of the propagating signal. The intensity fluctuation spectra of the harmonic components of the response are obtained for the frequency range of 10⁻⁴−10⁻¹ Hz. A possible mechanism that may be responsible for the slow fluctuations of an acoustic field in a granular medium is discussed.

     

Dipole moments of triethyl(phenoxy) derivatives of Group IVB elements in ground and electronically excited states

Russian Chemical Bulletin - The dipole moments of the trialkyl(phenoxy) derivatives of the Group IVB elements in the ground and first singlet excited states show that in the excited state the...     

On the influence of the Reynolds number on the intensity of vortex sound flowing around a cylindrical profile

Regularities of the emission of vortex sound (eolian tone) during air flow around stationary and rotating cylindrical profiles have been investigated. The influence of the flow Reynolds number on the intensity of vortex sound emission has been estimated from results of measuring the pressure fluctuation distribution on the surface of stationary cylindrical rods flowed around by air, as well as in the wake behind them. It is shown that the emission intensity depends on the location of the point of flow detachment from the profile surface and the track width near the profile. The ranges of the flow Reynolds numbers where the emission intensity increases with different flow velocities have been determined by analyzing the dependence of the profile lift coefficient on the Reynolds number. An independent way of determining the profile lift coefficient by measuring the vortex sound intensity is proposed. The results explain contradictions between the results of some authors, who experimentally observed different dependences of emission intensity on the flow velocity. The influence of the profile diameter on the vortex sound emission intensity has been investigated. The boundary Reynolds number above which the profile diameter does not affect emission has been established for stationary and rotating cylindrical profiles. It is shown that deposition of rough coatings on the rod surface may reduce the vortex sound emission intensity by affecting the point of flow detachment from the surface.     

Nature of the source of vortex sound flowing around a cylindrical profile

This paper is devoted to refining the nature of a vortex sound source and validly estimating the parameters of the region of source origination in a wake behind a cylindrical profile depending on the incoming flow velocity and profile diameter. Based on experimental measurements of the rms values of pressure pulsations on the surface and in the wake behind the profile and hydrodynamic laws for 2D fluid flows, the position of the origin of the vortex street in the wake and the size of the region where the street is still irregular are estimated. In this region, the street dimensions and pressure pulsation amplitudes change with distance from the profile. It is found that the maximum of the pressure pulsation in the wake approaches the profile surface in the range of Reynolds numbers (4.7 × 10³?1.5 × 10⁴); the amplitude of pressure pulsations on the profile and vortex sound intensity also increase. Based on the relationship between the source’s position and size and the width of the vortex street, as well as taking into account the decay of vortex circulation in the street with increasing distance to the profile, it is shown that the distance from the source to the surface of the profile should not exceed two gages. It is shown that an obstacle in the wake in the region of its irregularity causes a decrease in pressure pulsations on the profile and attenuation of emitted sound. Sound emission ceases completely when the obstacle comes in direct contact with the region of origination of the vortex street. Theoretical estimates satisfactorily agree with the measurement results.     

Effect of the acidity and chemical nature of the protonating agent on the rate of acetylene reduction catalyzed by the nitrogenase active site isolated from the enzyme

The effect of the acidity (pK _a) of the source of protons on the rate and selectivity of acetylene reduction has been investigated in order to elucidate the mechanism of protonation of substrate molecules coordinated to the reduced FeMoco cluster. A number of compounds whose pK _a in DMF varies between 6 and 20 have been examined as protonating agents. The rate of the reaction is almost independent of the acidity of the proton donor in a wide pK _a range. This can be explained in terms of the specific features of substrate protonation catalyzed by iron-sulfur clusters. Active protonating agents in the system are those which react with the catalyst to form hydrogen-bonded association species or those which are ligands reversibly binding to the cluster and are capable of donating protons, likely with simultaneous electron transfer.