N2O5 photolysis products investigated by fluorescence and optoacoustic techniques

Pulsed laser photolysis of N₂O₅ near 290 nm coupled with fluorescence detection (calibrated by NO₂ photolysis) showed that the O(³P) quantum yield is ≤0.1. A pulsed laser optoacoustic technique in a flow tube (ca. 6 torr of N₂) was tested by photolysis of NO₂ and then applied to N₂O₅. Nitric oxide was added to react with NO₃ free radical and the resulting increase in the optoacoustic signal confirmed the presence of NO₃ free radicals. Based on the relative optoacoustic signals observed for NO₂ and N₂O₅, the quantum yield for NO₃ production is 0.8 ± 0.2.     

High temperature collisional energy transfer in highly vibrationally excited molecules: Isotope effects in tert-butyl chloride systems

The average downward collisional energy transfer (<ΔE_down>) is obtained for highly vibrationally excited tert-butyl chloride, both undeuterated and per-deuterated, with Kr, N₂, CO₂, and C₂H₄ bath gases, at ca. 760 K. Data are obtained using the technique of pressure-dependent very low-pressure pyrolysis. Reactant internal energies to which the data are sensitive are in the range 200–250 kJ mol^?1. For C₄H₉Cl, the <ΔE_down> values (cm^?1) are 255 (Kr), 265 (N₂), 440 (CO₂), and 585 (C₂H₄), and for C₄D₉Cl, 245 (N₂), 370 (CO₂), and 540 (C₂H₄). The uncertainties in these values are ca. 20% (40% for Kr); the uncertainties in the deuteration ratios are 10–15%. The value for Kr is in agreement with theoretical predictions of a biased random walk model for internal energy change in monatomic/substrate collisions. The effect of deuteration of <ΔE_down> is also in accord with that predicted by a modification of the theory. Extrapolated highpressure rate coefficients for the thermal decomposition of reactant are 10^13.6 exp(-187 kJ mol^?1/RT) s^?1 (C₄H₉Cl) and 10^14.2 exp(?196 kJ mol^?1/RT) s^?1 (C₄D₉Cl), in accord with other studies and the expected isotope effect.     

Crystallographic studies and semi-empirical MNDO calculations on quisqualic acid and its analogues: Systems containing unusual pyramidal heterocyclic ring nitrogens

Summary X-ray crystallographic studies on synthetic DL-quisqualic acid and the corresponding carbon analogue have revealed pyramidal and almost planar geometries respectively for the ring nitrogen atoms carrying the alkyl side chain. Semi-empirical molecular orbital calculations on methyl-substituted model systems predict ring geometries in close agreement with experimentally observed data. The calculated energy barriers between the two enantiomeric forms (invertomers) of the oxadiazolidine systems along with some physical data would suggest that such forms are rapidly interconverting.Deceased.     

Incorporation of a new alkenyl‐based nonionic surfmer into acrylic latexes

The mechanisms by which a new nonionic alkenyl‐based surfmer (Maxemul 5011?) was involved in acrylic emulsion polymerization were investigated. No proof of homopolymerization or of chain transfer to surfmer was obtained under the conditions studied. The effect of the initiator type, feeding time of the surfmer, particle size of the seed, and surfmer concentration, on kinetics and surfmer incorporation showed that the surfmer reacted mainly by copolymerization with the monomers in the outer shell of the polymer particles. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4202–4211, 2004     

Acetylation of a heterocyclic enaminonitrile: Unambiguous structural assignment using NMR methods

Using a combination of nmr techniques, the structure of the acetylation product of methyl 3-[2-amino-3-cyano-9-methoxy-4H-5,6-dihydronaphtho[1,2-b]pyran-4-yl] benzoate 2b has been shown to be the N-acetyl derivative 5a , rather than the rearranged 2-acetoxydihydropyridine 6a.     

Manganese Catalyzed Hydrogenation of Organic Carbonates to Methanol and Alcohols

The first example of a homogeneous catalyst based on an earth‐abundant metal for the hydrogenation of organic carbonates to methanol and alcohols is reported. Based on the mechanistic investigation, which indicates metal‐ligand cooperation between the manganese center and the N?H group of the pincer ligand, we propose that the hydrogenation of organic carbonates to methanol occurs via formate and aldehyde intermediates. The reaction offers an indirect route for the conversion of CO₂ to methanol, which coupled with the use of an earth abundant catalyst, makes the overall process environmentally benign and sustainable.     

Two-rowed Hecke algebra representations at roots of unity

In this paper, we initiate a study into the explicit construction of irreducible representations of the Hecke algebraH _n (q) of typeA _n-1 in the non-generic case whereq is a root of unity. The approach is via the Specht modules ofH _n (q) which are irreducible in the generic case, and possess a natural basis indexed by Young tableaux. The general framework in which the irreducible non-genericH _n (q)-modules are to be constructed is set up and, in particular, the full set of modules corresponding to two-part partitions is described. Plentiful examples are given.Presented at the 4th International Colloquium Quantum Groups and Integrable Systems, Prague, 22–24 June 1995.     

Electrocatalysis at graphite and carbon nanotube modified electrodes: edge-plane sites and tube ends are the reactive sites

Carbon, and particularly graphite in its various forms, is an attractive electrode material. Two areas of particular interest are modified carbon electrodes and carbon nanotube electrodes. In this article we focus on the relationship between surface structure and electrochemical and chemical reactivity of electrodes based on these materials. We overview recent work in this area which has led us to believe that much of the catalytic activity, electron transfer and chemical reactivity of graphitic carbon electrodes is at surface defect sites, and in particular edge-plane-like defect sites. We also question the claimed special "catalytic" properties of carbon nanotube modified electrodes.     

Activity coefficients at infinite dilution measurements for organic solutes in the ionic liquid 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide using g.l.c. at T = (298.15, 313.15, and 333.15) K

The activity coefficients at infinite dilution, (where 1 refers to the solute and 3 to the solvent), for both polar and non-polar solutes (alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, benzene, carbon tetrachloride, and methanol) in the ionic liquid 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide [HMIM][Tf₂N] at three temperatures T = (298.15, 313.15, and 333.15) K have been determined by gas-liquid chromatography. The interaction at the gas-liquid interface between the solutes and the solvent was examined by varying solvent liquid loading on the column. Corrected retention values, taking carrier gas and solute imperfections into account, were determined and used to calculate the activity coefficients at infinite dilution. The results have been used to predict the solvent potential for the hexane/benzene separation from calculated selectivity values. The results were compared to for similar systems found in the literature in an attempt to understand the effect of the nature of the cation and anion has on solute-solvent interactions.The partial molar excess enthalpies at infinite dilution values were calculated from the experimental values obtained over the temperature range.