Interaction of a low-pressure gas flame and heterogeneous catalytic processes on the reactor surface

Conclusions (1) It was shown that the Semenov theory in various modes of chain termination quantitatively describes oxyhydrogen combustion near the first ignition limit with allowance for the interaction between the flame and the catalytic processes on the reactor wall. (2) Numerical modeling of oxyhydrogen ignition in the diffusion-controlled chain-termination mode detected the dependence of the rate “constant” for heterogeneous chain initiation on the model of the reaction in the gas. (3) For the first time, the change in the specific rate of heterogeneous chain initiation during a single ignition was determined. (4) method for controlling the low-pressure flame mode by affecting tubes far from the reactor was proposed and applied. Original Russian Text ? E.N. Aleksandrov, S.N. Kozlov, N.M. Kuznetsov, 2006, published in Doklady Akademii Nauk, 2006, Vol. 407, No. 5, pp. 630–633. Presented by Academician A.E. Shilov October 5, 2005     

Theory of electron tunneling through a bridge molecule with two electronic levels at low temperatures

A theory of electron tunneling through a single-center bridge redox group that has two electronic levels participating in the electron transfer process is presented. The temperature is presumed to be low enough to ignore activation redox conversions of the bridge group. Salient features of this system are due both to the presence of two electroactive states of the bridge group and to relaxation processes along the reaction coordinate. The processes in question make the tunneling current time-dependent at fixed potentials and can bring about hysteresis in current-voltage curves when cycling the bias potential. Effects of inelastic tunneling with excitation of vibrations of a local quantum degree of freedom are considered.     

The free energy gap and temperature dependence of the electronic transmission coefficient in electron-transfer reactions of the solvated electron

We have investigated the dependence of the electronic factor in electron-transfer rate constants on the energy gap and temperature by minimizing the electronic energy with respect to the instantaneous non-equilibrium solvent polarization. The electronic charge billows out and shrinks in the “normal” and strongly exothermic free energy region, respectively, but the effect is only comparable to the variation of the nuclear factor for low temperatures and strongly exothermic processes.     

Transformations ofmyo-inositol hexa-O-nitrate under the action of amines

Reactions ofmyo-inositiol hexa-O-nitrate with ammonia and primary amines yield tetrahydroxy-1,4-benzoquinone derivatives,viz., its tetraammonium salt and its diimines, respectively. Reactions with secondary and tertiary amines give salts of rhodizonic acid, which are converted into salts of croconic acid under certain conditions. The reactions with secondary amines involve intermediate formation of radical species, which were dectected by ESR spectroscopy. A scheme for the chemical transformations ofmyo-inositol hexa-O-nitrate under the action of amines was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2962–2967, December, 1996.     

Anomalous reaction of 1-ethyl(benzyl)-3-methyl-2-benzopyrylium salts with dimethylamine

Chemistry of Heterocyclic Compounds -