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.     

Structure of fullerene-containing soot at different formation stages of arc discharge vaporization of graphite

Electron microscopy is used in a study of nanoclusters of the carbon soot deposited on a probe in different areas of arc discharge during graphite vaporization under conditions favorable for fullerene synthesis. It is found that the spatial network of soot nanoclusters consists of alternating regions of higher density or associates of carbon particles. Two types of nanoclusters have been identified with the correlation radii of the associates equal to 0.6–0.8 and 1.6–2.2 nm, respectively. Type I nanoclusters are dominant in the soot microparticles, and their structure shows practically no variations with increasing separation r of the soot collector from the discharge axis over the range of distances studied, r=1–9 cm. The effective radius R ₀ of the “elementary” particles making up the associates in the soot nanoclusters of Type I calculated with the use of scaling relationships is 0.15–0.17 nm and is close to the gas-kinetic radius of carbon atoms. Type II nanoclusters have been identified in soot collected at r>3 cm. Values of R ₀ calculated in this case are 0.6–0.9 nm and decrease with increasing r, which indicates the presence of fullerene molecules in these nanocluster associates.     

A note on inverses in arithmetic with fuzzy numbers

Algorithms for systematical search of inverse in arithmetic operations with fuzzy numbers are discussed. The fuzzy number derived is considered either in a discrete representation of its support or described by the parameters of the corresponding membership function formula. Both algorithms are easy to be programmed for desk calculators.     

On worst-case aggregation analysis for network location problems

Network location problems occur when new facilities must be located on a network, and the network distances between new and existing facilities are important. In urban, regional, or geographic contexts, there may be hundreds of thousands (or more) of existing facilities, in which case it is common to aggregate existing facilities, e.g. represent all the existing facility locations in a zip code area by a centroid. This aggregation makes the size of the problem more manageable for data collection and data processing purposes, as well as for purposes of analysis; at the same time, it introduces errors, and results in an approximating location problem being solved. There seems to be relatively little theory for doing aggregation, or evaluating the results of aggregation; most approaches are based on experimentation or computational studies. We propose a theory that has the potential to improve the means available for doing aggregation.This research was supported in part by the National Science Foundation, Grant No. DDM-9023392.     

A Simulation Study of Due-date Assignment Rules in a Dynamic Job Shop

This paper is a report of a simulation study that investigates a dynamic approach to scheduling jobs in a multi-machine job shop. The workload information of a job is used in different forms to evaluate the shop performance based on three measures: mean job lateness, percentage of tardy jobs and lateness variance. Different combinations of due-date assignment methods and sequencing rules are compared based on specific performance criteria. The results indicate that using the cumulative distribution function of workload information can yield a better performance than using a proportional function of workload information or ignoring shop congestion information. A few situations are identified in which workload information is not critical.     

Separation of screw-sensed particles in a homogeneous shear field

The Stokes motions of three-dimensional screw-sensed slender particles in a homogeneous shear field are investigated, including the effects of buoyancy. Conclusions are drawn about the possibility of achieving a separation of mixtures of right- and left-handed particles. The linearity of the Stokes equations allows complex flows to be solved by adding the effects of the several terms which describe the flow in which the particle is immersed. The homogeneous shear flow considered here consists of three such terms; solutions for a series of 12 unit motions are sufficient to determine the hydrodynamic resistance tensors. The forces and torques experienced by screw-sensed particles are calculated from these 51 resistance tensors, using slender-filament theory. The results allow an estimate of the range of buoyancy parameters for which gravitational sedimentation can be neglected. The fundamental component of the particle motion is a rotation, at approximately the same angular velocity as that of the fluid. Superimposed on this are variations, of large period, in the particle orientation. A phase plane analysis is used to find the terminal orientations. Very long calculation times are required for the phase portrait. An approximate method based on azimuthally-averaged equations is developed to avoid the requirements for long time integration.     

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.