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.     

Development of the Bogolyubov-Mitropol'skii method of integral manifolds

A survey is presented of some results relating to the development of the Bogolyubov-Mitropol'skii method of integral manifolds.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 44, No. 1, pp. 33–46, January, 1992.     

Mössbauer gamma echo

By applying stepwise phase modulation of recoilless gamma radiation in a coincidence experiment, constructive interference is produced in transmission geometry between the source and the absorber fields. The resulting regenerated decay signal is called a gamma echo. Here it is demonstrated that during the decay of the 14.4 keV state of⁵⁷Fe multiple echo signals can be generated.     

Single-molecule single crystals

Various approaches to the preparation and verification of single-molecule single crystals are discussed for polyethylene and poly (oxyethylene). Analytic tools are electron microscopy, electron diffraction, and differential scanning calorimetry. The main difficulty in producing a single-molecule single crystal is to keep crystals from joining during growth.     

The exponential characteristic of the Volterra integral operator with kernel depending on 2<Emphasis Type="Italic">N</Emphasis> variables

Exponential growth is estimated for integral operators with continuous periodic kernels of exponential type. The result is applied to the boundary-value problem for a general hyperbolic differential equation having periodic coefficients with Goursat boundary conditions. It is proved that the exponential characteristic for such a boundary-value problem has canonical form. __________ Translated from Sovremennaya Matematika i Ee Prilozheniya (Contemporary Mathematics and Its Applications), Vol. 38, Suzdal Conference-2004, Part 3, 2006.     

Adsorption of nonionic surfactant triton X-100 on solids from aqueous and nonaqueous solutions

The adsorption of nonionic surfactant Triton X-100 on quartz sand and methylated quartz sand from water and toluene was investigated by means of spectrophotometry, the radiotracer technique, and wetting angle measurements.     

Differentiation of species of the Baccharis genus by HPLC and chemometric methods.

Phytochemical investigation of the aerial parts of three Baccharis species (Asteraceae family) was performed using HPLC and chemometric methods, with the objective of distinguishing between three morphologically very similar species: Baccharis genistelloides Persoon var. trimera (Less.) DC, B. milleflora (Less.) DC and B. articulata (Lam.) Persoon. With the help of Principal Component Analysis (PCA) and variance weights, it was possible to characterize the chromatographic profiles of the alcoholic extracts of the three species. Application of Soft Independent Modeling of Class Analogy (SIMCA) and K-Nearest Neighbor (KNN) methods on a training set of 74 extracts resulted in models that correctly classified all eight samples in an independent test set.     

Diffuse x-ray scattering study of the formation of microdefects in heat-treated dislocation-free large-diameter silicon wafers

Diffuse x-ray scattering (DXS) is used to study the formation of microdefects (MDs) in heat-treated dislocation-free large-diameter silicon wafers with vacancies. The DXS method is shown to be efficient for investigating MDs in silicon single crystals. Specific defects, such as impurity clouds, are found to form in the silicon wafers during low-temperature annealing at 450°C. These defects are oxygen-rich regions in the solid solution with diffuse coherent interfaces. In the following stages of decomposition of the supersaturated solid solution, oxide precipitates form inside these regions and the impurity clouds disappear. As a result of the decomposition of the supersaturated solid solution of oxygen, interstitial MDs form in the silicon wafers during multistep heat treatment. These MDs lie in the {110} planes and have nonspherical displacement fields. The volume density and size of MDs forming in the silicon wafers at various stages of the decomposition are determined.