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.     

Interdiffusion of hydroxyl groups and of doping additions between a bearing pipe and a deposited layer in billets of fiber light guides

Using Raman spectroscopy, a quantitative analysis of the distribution of OH⁻ ions on the boundary between a bearing pipe and a glass layer deposited from chlorides in billets for quartz fiber light guides is carried out. Water penetrated into the light-reflecting shell to a depth of several tenths of a millimeter, depending on the composition of the doping layer (i.e., ultimately on the temperature of the depsoition process). A. F. Ioffe Physical-Technical Institute, Academy of Sciences of Russia, 26, Politekhnicheskaya St., St. Petersburg, 194021, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 548–550, July–August, 1997.     

Cores and retracts

Theretracts (idempotent, isotone self-maps) of an ordered set are naturally ordered as functions. In this note we characterize the possible ways that one retract can cover another one. This gives some insight into the structure of the ordered set of retracts and leads to a natural generalization of the core of an ordered set.Supported by NSERC Operating Grant 41702.     

Solution of the planar linear filtration problem in layered soils

Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, No. 6, pp. 119–122, November–December, 1991.     

The inclusion of electrostatic and dispersion interactions into potentials of mean torque for solutes dissolved in uniaxial liquid crystal solvents

A potential of mean torque is derived for a solute at infinite dilution in a uniaxial liquid crystal solvent, which contains terms originating from the dispersion interaction, and the electrostatic interaction between quadrupole moments on both molecules. It is shown that the electrostatic term is non-zero only if the solute-solvent vectors are distributed with lower than spherical symmetry. If this distribution has cylindrical symmetry then both the electrostatic and dispersion terms in the potential of mean torque are shown to depend on order parameters for the orientational distribution of the solute-solvent vectors, as well as on the order parameters of the solvent molecules.     

Electronic phase separation in a low-temperature tetragonal phase of lanthanum-strontium cuprates according to 139La NQR data

A nonuniform electron density distribution is observed in La_{1−x− y} Nd_ySr_xCuO₄ and La_1−x−y Eu_ySr_xCuO₄, and long-lived magnetic fluctuations in these compounds are studied. The dynamics of the magnetic fluctuations depends strongly on the magnetic properties of the rare-earth ions, which stabilize the low-temperature tetragonal phase. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 5, 344–349 (10 March 1998)