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.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

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.     

Evaluation of peroxyoxalate chemiluminescence postcolumn detection of fluphenazine in urine and blood plasma using high performance liquid chromatography

Peroxyoxalate chemiluminescence may be used for sensitive postcolumn detection of phenothiazine analytes separated by high performance liquid chromatography with appropriate optimization of measurement conditions such as solvent, pH and oxalate ester. Detectability of fluorescent analytes by chemical excitation varies greatly, but analytes with low oxidation potentials are generally more readily detected at low levels, as demonstrated for phenothiazines, an important class of fluorescent drugs. Some improvement in detection limits is observed for fluphenazine when chemiluminescence detection is compared to conventional fluorescence detection. Because of the specificity of chemical excitation, fewer interferences from fluorescent impurities in a urine matrix are observed.