Evolution of the q-entropy and energy dissipation during irreversible processes in nonextensive systems

Evolution of the Havrda-Charvat-Daroczy entropy and energy dissipation during irreversible processes in open nonextensive systems is considered. The kinetic equation and statistical criterion of nonextensive system evolution are presented. Nonequilibrium statistical and variational methods of derivation of the kinetic equation with a source being a fluctuation of a physical quantity are described. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 35–41, February, 2006.     

Electrochemically induced processes in the formation of phosphorus acid derivatives. 1. Synthesis of trialkyl phosphates from white phosphorus

An electrochemical method, based on the joint action of nucleophilic and electrophilic reagents on P₄, is proposed in order to utilize white phosphorus in the formation of the esters of phosphorus acids. The action of alkoxide ions on white phosphorus in an alcohol medium in the presence of iodine generated at the anode leads to the formation of phosphate esters. A scheme in which the intermediate products are dialkyl and trialkyl phosphites and the side product is dialkyl alkylphosphonate is proposed for the process.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420028 Kazan'. V. I. Ul'yanov-Lenin Kazan State University, 420028 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1322–1328, June, 1992.     

Determination of enthalpies of formation of organic free radicals from bond dissociation energies 1. Hydrocarbon radicals

The enthalpies of formation (ΔH _f ^o) for 24 hydrocarbon radicals (R^?), mainly polycyclic aromatic radicals with the complex structure, were determined from the published data on bond dissociation energies. The ΔH _f ^o values of the corresponding molecules were calculated, in the majority of cases, by the macroincrement method. Calculations by the group contribution method were performed. Some ΔH _f ^o(R^?) values were compared to those calculated by the additive-group method. Calculations were performed, and the conjugation energies of the radicals were discussed. The errors of determination of the ΔH _f ^o(R^?) values found were estimated. Due to this work, the database for ΔH _f ^o values of hydrocarbon radicals was increased more than by 25%.     

Modeling of Electrochemical Copying in a Finite-Width Cell

The problem of modeling of electrochemical machining is reduced to the solution of the Schwartz problem on a parametrical rectangle with the use of theta-functions. Various conditions (non-equipotentiality of electrodes and inconstancy of current efficiency) at the boundary of a processed surface are considered. Nonstationary, quasistationary, stationary, and limit solutions are studied. Results of machining of surfaces by tool electrodes of various shapes are given. It is shown that machining mode parameters significantly affect the dissolved layer size necessary for obtaining high-precision copying.     

<Superscript>1</Superscript>H and <Superscript>31</Superscript>P nuclear spin-lattice relaxation in C-phosphorylated oximes

The ¹H spin-lattice relaxation times of the proton-bearing groups and the ³¹P spin-lattice relaxation times in C-phosphorylated oximes R¹C(=NOH)P(=O)R²R³ (R¹ = Ph, R² = R³ = OMe; R¹ = Ph, R² = OMe, R³ = OCH²CH²Br; R¹ = PhCH², R² = R³ = OCHMe²) and dioxime R²P(=O)C(=NOH)(CH₂)₄C(=NOH)P(=O)R² (R = OMe) in DMSO-d₆ were measured. The characteristic reorientation times of the whole molecules were estimated using the measured values of the ¹H relaxation times and the results of semiempirical PM3 quantum chemical calculations of the molecular geometries. The reorientation times were used to identify the contributions of different relaxation mechanisms to the rate of ³¹P spin-lattice relaxation. The anisotropy of the chemical shielding of ³¹P nuclei was evaluated from the difference between the ³¹P relaxation rates measured at 101.27 and 161.92 MHz.     

Molecular structure of 2-bromo-1,3,2-dioxarsenane

A calculation was carried out for the normal mode frequencies and forms of 2-bromo- and 2-chloro-1,3,2-dioxarsenanes. Gaseous electron diffraction was used to determine the r_a structure of 2-chloro-1,3,2-dioxarsenane. In accord with the results of other physical measurements, we established the chair conformation with axial orientation of the bromine atom.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 5, pp. 55–60, September–October, 1989.