Optical diagnostics of dispersing He plasma

An experimental study has been made of the characteristics of radiation from a dispersing helium plasma. From measurements of the space-time dependence of the line intensities of the helium 2³P — n³D series we obtained the distribution of the populations of the n³D levels for n=3–10. The study has shown that over a wide range of conditions the high-lying levels (n=5–10) are in equilibrium with electrons while a substantial deviation from equilibrium is observed for levels n=3, 4. From the energy distribution of the populations of the upper levels we determined the space-time dependence of the electron temperature, which reflects the process of effective electron cooling during dispersal of the plasma. The gas temperature was estimated from the populations of helium singlet and triplet levels with n=5. The time distribution of the electron density in the plasma was found from the Stark broadening of the spectral lines.Deceased.V. D. Kuznetsov Siberian Physicotechnical Institute, Tomsk State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 15–19, November, 1992.     

Density functional taking into account nuclear thermal motion of compressed matter

Bogolyubov's inequality is used to generalize the density functional method to take into account nuclear thermal motion. The results apply to a two-component system in which the nuclei satisfy classical statistics. Applications to a cell model describing dense heated states of matter are considered.All-Union Research Institute of Opticophysical Measurements of the USSR State Standards. Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 92, No. 1, pp. 154–157, July, 1992.     

Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate.     

Certified reference materials for the quality control of analysis in the environment

Summary The Community Bureau of Reference (BCR) has undertaken the production of a wide range of certified reference materials (CRMs) for the improvement of accuracy and measurement harmony in various areas of concern at European Community level. This paper provides an overview of the sectors of the BCR-programme in the field of environment i.e. for water systems (water, sediment, biota), soil analysis (soil, fertiliser, waste), plant analysis (aquatic and terrestrial plants), analysis related to animals (e.g. muscle or liver) or man (e.g. industry and food).     

Mössbauer studies of iron uptake,ferritin and hemoglobin synthesis and denaturation in erythroid cell cultures

Mössbauer studies in murine (MEL) and human K-562 erythroleukemia cell lines have been utilized to study the fate of iron during intracellular Hb synthesis and denaturation. The results showed that ferritin can serve as an intermediate iron pool for Hb synthesis and for storage of iron released during intracellular Hb denaturation.     

Microscopic theory of vitrification of metallic solutions

A Green's function technique is developed for describing compositional ordering and vitrification of solid solutions with arbitrary composition. It is shown that the proposed approach is related with the standard theory of ordering of regular solid solutions. Peculiarities of the diagrammatic technique are studied. Explicit expressions are derived for the spectrum of solitary excitations, which are responsible for the ordering. Equations are derived for determining the temperature-concentration dependences of the compositional order parameter, the vitrification parameter, and the chemical potential.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 60–65, May, 1991.     

Identification of low-energy light nuclei recorded by means of an ionizational mass spectrometer

A method of identifying low-energy nuclei from the readings of an ionizational mass spectrometer is considered. The identification principles for particles recorded by a multilayer detector are discussed, together with the fundamentals of a probabilistic approach to the solution of this problem. The method permits correct analysis of the experimental data obtained. The determination of the charge and isotopic composition of radiation consisting of a mixture of different nuclei is considered. The results of calculations by the given method which permit the determination of the optimal detector parameters for the solution of the specific physical problem are outlined. This approach is also applicable for the analysis of data from other types of measuring apparatus.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 84–88, July, 1991.     

Temperature dependence of the rate constants for reactions of the carbonate radical with organic and inorganic reductants

Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO₃^·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of Fe^II, Mo^IV, and W^IV, the simple inorganic anions SO₃^2?, ClO₂^?, NO₂^?, I^?, and SCN^?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 10⁵ to 3 × 10⁹ M^?1 s^?1, the activation energies ranged from ?11.4 to 18.8 kJ mol^?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.