Isotopic study of the mechanism of ozone formation

The mechanism of ozone formation has been studied using ¹⁶O and ¹⁸O₂. High-resolution microwave spectroscopy was used to measure the amounts of the isotopomeric ozone species formed. The study is hampered by the very rapid exchange process between the reactants, that tends to scramble the isotopes and hence give a 2:1 statistical ratio between the two possible isotopomers. We have found a strategy to come around this difficulty and conclude that the mechanism is a simple end-on-addition.     

Kinetic study of n-heptane oxidation

The oxidation of n-heptane has been studied in a jet-stirred flow reactor in the temperature range 950–1200 K at atmospheric pressure for a wide range of fuel-oxygen equivalence ratios (0.2 to 2.0). A chemical kinetic reaction mechanism developed from previous studies on smaller hydrocarbons and extended to C₆ and C₇ species was used to reproduce the experimental data. Good agreement between computed and measured concentrations of major chemical species was obtained for the entire range of experimental conditions. Sensitivity analyses were carried out to identify the reactions having the greatest influence on the modeling results. The major reaction paths for n-heptane consumption and for the formation of the main products have been identified. In addition n-heptane ignition delays behind a reflected shock wave measured by other investigators were used to validate the present reaction mechanism at higher temperature and pressure.     

Deformations of complex structures on Γ/SL 2(C)

LetG be a connected complex semisimple Lie group. Let Γ be a cocompact lattice inG. In this paper, we show that whenG isSL ₂(C), nontrivial deformations of the canonical complex structure onX exist if and only if the first Betti number of the lattice Γ is non-zero. It may be remarked that for a wide class of arithmetic groups Γ, one can find a subgroup Γ′ of finite index in Γ, such that Γ′/[Γ′,Γ′] is finite (it is a conjecture of Thurston that this is true for all cocompact lattices inSL(2, C)). We also show thatG acts trivially on the coherent cohomology groupsH ⁱ(Γ/G, O) for anyi≥0.     

On composition of some general fractional integral operators

In the present paper we derive three interesting expressions for the composition of two most general fractional integral oprators whose kernels involve the product of a general class of polynomials and a multivariableH-function. By suitably specializing the coefficients and the parameters in these functions we can get a large number of (new and known) interesting expressions for the composition of fractional integral operators involving classical orthogonal polynomials and simpler special functions (involving one or more variables) which occur rather frequently in problems of mathematical physics. We have mentioned here two special cases of the first composition formula. The first involves product of a general class of polynomials and the Fox’sH-functions and is of interest in itself. The findings of Buschman [1] and Erdélyi [4] follow as simple special cases of this composition formula. The second special case involves product of the Jacobi polynomials, the Hermite polynomials and the product of two multivariableH-functions. The present study unifies and extends a large number of results lying scattered in the lierature. Its findings are general and deep.     

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.     

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.