Determination of the regime in the reverse wilson chamber at critical supersaturation measurements

The pressure in the Reverse Wilson Chamber (RWC) was directly measured at different rates of compression of the gas mixture. It was shown that at compression time in the range from 0.06 to 0.3 s an intermediate, between adiabatic and isothermal, process took place in the chamber. To obtain the relative pressure increase P _m /P _at from the values of the relative gas compression V/V, a calibration of the experimental set-up was carried out. The calibration showed that the values of critical supersaturationSc for water condensation on hexadecane, estimated for intermediate regime of the gas compression, were reduced with respect to the values calculated when the adiabatic regime was assumed. This fact confirmed the conclusions made earlier [1–3] that the classical theory was not applicable in this case of heterogeneous phase formation and that the line tension < 0 should be taken into account. Moreover, in an atmosphere of very pure argon (instead of room air [1–3]) the critical supersaturation turned out to be independent of the initial state of undersaturationS _o . The more accurate values obtained for condensation of water on hexadecane were: lnS _c =0.204 (instead of the maximum value obtained earlier: lnS _c =0.26) and=–1.9×10^–5 dyne (instead of=–1.5×10^–5 dyne).     

Synthesis and study of catalysts of electrochemical oxygen reduction reaction based on polymer complexes of nickel and cobalt with Schiff bases

The article presents the results of studies of new nanosize catalysts of electrochemical oxygen reduction reaction (ORR) obtained using the method of thermal decomposition of polymer complexes of nickel and cobalt with tetradentate (N₂O₂) Schiff bases. The catalysts are characterized using the methods of thermogravimetry, electrochemical quartz microgravimetry, scanning electron microscopy with X-ray microanalysis, XPS. The ORR process on electrodes modified by the above catalysts was studied using the voltammetry and rotating disk electrode techniques. The obtained catalysts manifested high specific activity per initial polymer mass (more than 600 mA/mg).     

Unusual synthesis,structure, and thermochromic properties of novel sterically hindered cyclohexadienes

Oxidation of 4-[-morpholino--(2-hydroxyphenyl)]methyl-2,6-di-(tert-butyl)-phenol (I) follows an unusual course, with formal loss of the benzyl carbon atom, to give 2,6-di(tert-butyl)-4-morpholino-4-(2-hydroxyphenyl)cyclohexa-2,5-dienone (II), which is thermochromic in solution. This property is due to the dissociation of (II) into morpholine and 3,5-di(tert-butyl)-2,4-diphenoxyquinone. The structure of (II) was established directly by x-ray diffraction, which enabled its conformational features to be related to its thermochromic properties. An x-ray examination of 3,3,5,5-tetra(tertbutyl)-2,4-diphenoquinone (X), together with the direct synthesis of the thermochromic analog of (II) (2,6-di(tert-butyl)-4-morpholino-4-[2-hydroxy-3,5-di(tert-butyl)phenyl]cyclohexa-2,5-dienone) (XI) from (X) and morpholine, confirmed the proposed mechanism of thermochromic dissociation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1121–1129, May, 1991.The authors thank V. I. Minkin and A. S. Morkovnik for participating in discussions of this work.     

Theory of locking of a Van der Pol oscillator by delayed reflection from a resonant load

We use methods of dynamic theory [1–3] to describe how a weak, but properly phased delayed reflection from a high-Q resonant load holds the frequency of a self-excited oscillator within the load frequency band. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 49, No. 6, pp. 537–551, May 2006.     

Crystal and molecular structure of the hydroxonium salt of sulfoisophthalic acid

L. Ya. Karpov Physicochemical Scientific Research Institute. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 3, pp. 174–177, May–June, 1989.     

Minimal covering problem and redundancy reduction in databases

One of the main problems in efficient organization of a database system is minimization of the redundancy of information. In this paper, we enumerate the causes of redundancy and reduce the problem of redundancy minimization to the minimum covering problem. This requires inclusion in the database management system of a module for aggregation of data elements into larger constructs — segments, records, files. The module can be software or hardware implemented. Regardless of its implementation, the module has the structure of a 0–1 matrix, which can be transformed by the standard methods of block matrices. A compression algorithm is proposed, which reduces the redundancy introduced by the designer or by the users in single and multiuser queries.Translated from Vychislitel'naya i Prikladnaya Matematika, No. 64, pp. 141–144, 1988.     

Experimental and density functional theoretical investigations of linkage isomerism in six-coordinate FeNO(6) iron porphyrins with axial nitrosyl and nitro ligands

A critical component of the biological activity of NO and nitrite involves their coordination to the iron center in heme proteins. Irradiation (330 < lambda < 500 nm) of the nitrosyl-nitro compound (TPP)Fe(NO)(NO(2)) (TPP = tetraphenylporphyrinato dianion) at 11 K results in changes in the IR spectrum associated with both nitro-to-nitrito and nitrosyl-to-isonitrosyl linkage isomerism. Only the nitro-to-nitrito linkage isomer is obtained at 200 K, indicating that the isonitrosyl linkage isomer is less stable than the nitrito linkage isomer. DFT calculations reveal two ground-state conformations of (porphine)Fe(NO)(NO(2)) that differ in the relative axial ligand orientations (i.e., GS parallel and GS perpendicular). In both conformations, the FeNO group is bent (156.4 degrees for GS parallel, 159.8 degrees for GS perpendicular) for this formally {FeNO}(6) compound. Three conformations of the nitrosyl-nitrito isomer (porphine)Fe(NO)(ONO) (MSa parallel, MSa perpendicular, and MSa(L)) and two conformations of the isonitrosyl-nitro isomer (porphine)Fe(ON)(NO(2)) (MSb parallel and MSb perpendicular) are identified, as are three conformations of the double-linkage isomer (porphine)Fe(ON)(ONO) (MSc parallel, MSc perpendicular, MSc(L)). Only 2 of the 10 optimized geometries contain near-linear FeNO (MSa(L)) and FeON (MSc(L)) bonds. The energies of the ground-state and isomeric structures increase in the order GS < MSa < MSb < MSc. Vibrational frequencies for all of the linkage isomers have been calculated, and the theoretical gas-phase absorption spectrum of (porphine)Fe(NO)(NO(2)) has been analyzed to obtain information on the electronic transitions responsible for the linkage isomerization. Comparison of the experimental and theoretical IR spectra does not provide evidence for the existence of a double linkage isomer of (TPP)Fe(NO)(NO(2)).     

Synthesis and Structure of Cobalt(III) Complex with Cyanomethylene and N,N′-Ethylenebis(3-methylsalicylideneiminate)

Russian Journal of General Chemistry - The new complex [CoIII(3-CH3Salen)(CH2CN)]·CH3CN was synthesized and its crystal structure was determined by the X-ray diffraction analysis. The...