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.     

Features of evolution of the substructure in the creep of dispersion-hardened nickel

A study is made of the laws governing high-temperature creep and the evolution of the substructure in dispersion-hardened alloy Ni — 3 vol. % HfO₂ during its free annealing and creep. The polygonized substructure was formed in the alloy prior to annealing. An analysis is made of structural transformations at different structural levels and the mechanism of high-temperature creep in the alloy. Institute of the Physics of Strength and Materials Science, Siberian Branch of the Russian Academy of Sciences. All-Republic Engineering-Technical Center, Siberian Branch of the Russian Academy of Sciences. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 83–89, March, 1998.     

Gauge theories for gravity on a line

In Memoriam M. C. Polivanov     

Plant processing by simultaneous lactic acid fermentation and enzyme hydrolysis

Traditional ensiling of plant material by anaerobic lactic acid fermentation was combined with enzymatic hydrolysis (ENLAC for short) with cell wall degrading enzymes (hemicellulases, cellulases, and pectinases) to increase fiber digestibility or to increase the recovery of cell content from plants. Such findings were made using 0.015% (w/w, wet basis) Phylacell® enzyme preparation by ENLAC of corn and corn-sorghum mixtures, but not of forage grasses. Addition to alfalfa of a mixture of cell wall degrading enzymes, such as NOVO Viscozyme® together with NOVO Celluclast® each at 0.2–1.0% (w/w, wet basis), resulted in more rapid ensiling and improvement of rumen digestibility of silage by 20%. After 20 d of ensiling at 25 °C when the same enzymes were added to alfalfa at the 1.0% level, protein recovery by pressing increased by 35%, β-carotene recovery by 80%, and chlorophyll/xanthophyll recovery by 30%. ENLAC with the same enzymes also increased the recovery of sclareol from muscatel sage by 400%.

     

Invariance of a system of automatic control

Utilizing the method of Lyapunov functions and matrix calculus, design of a nonlinear stable invariant system of automatic control is implemented. Sufficient conditions of invariance with precision up to e directly associated with the criterion of absolute stability of a system are obtained.Translated from Dinamicheskie Sistemy, No. 4, pp. 10–15, 1985.     

Capabilities and limits of ICP-MS for direct determination of element traces in saline solutions

An ICP-MS method for the determination of ultra-traces of 24 Elements (Li, Be, Mg, Al, Cr, Mn, Co, Zn, Cu, Ga, As, Se, Rb, Sr, Mo, Ag, Cd, Sn, Sb, Ba, Tl, Pb, Bi, U) at ng/L to μg/L levels in highly saline solutions (up to 30 g/L NaCl) was developed. Calculated to the salt content of the samples, limits of detection at the sub-μg/kg level were obtained. This allows the measurement of samples like sea water, or clinical samples like urine, serum and whole blood, with few or without sample preparation and a drastic improvement to the limits of detection. Compared to the determination in solutions of 1 g/L NaCl the limits of detection in the original sample were improved by one order of magnitude. Improvements in instrumental stability are achieved by the use of an additional gas, that is introduced to the aerosol stream and avoids salt deposition in the aerosol tube of the torch, the use of High Matrix Content (HMC) cones, that show no clogging even at NaCl-concentrations up to 50 g/L. With this setup the long term stability for measurements with changing matrix concentrations is < 10% without and < 5% with use of an internal standard for the individual samples. Cleaning up is necessary after 2 days of operation. The direct analysis of the Nearshore Seawater Reference Material NRC-CNRC CASS3 showed a good agreement with the certified and measured concentrations. Elements, that do not suffer from an isobaric overlap of matrix compounds can be determined clearly at ng/L levels. Measurement of different matrix concentrations showed, that acceptable results can be achieved with a single calibration for concentrations from 5 g/L NaCl to 30 g/L NaCl, though matrix matching shows the best results.     

Change in the nature of the Ni diffusion mechanism on the Si(111) surface with adsorption of Co atoms

The diffusion of Ni on a Si (111) surface is investigated by LEED and Auger electron spectroscopy. It is found that, in contrast to the process on the initially clean Si (111)−7×7 surface, on Si (111) surfaces with submonolayer Co coverages the nature of the Ni transport mechanism changes at a temperature of about 750 °C, and the Ni surface diffusion coefficients increase sharply below this temperature. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 9, 611–614 (10 November 1997)