Optical detection of NO3 and NO2 in “pure” HNO3 vapor,the liquid-phase decomposition of HNO3

Flowing and static gas-phase samples of HNO₃ in O₂ and N₂ were analyzed by long-path ultraviolet/visible (UV/VIS) spectroscopy to reveal the presence of both NO₂ and NO₃, the concentrations of which were calculated using differential absorption cross sections. NO₂ is produced predominantly by the heterogeneous decomposition of HNO₃, whereas NO₃ is generated in the gas phase by the thermal decomposition of N₂O₅, a product of the self-disproportionation of liquid HNO₃. © 1993 John Wiley & Sons, Inc.     

Ionic relaxation in nematic liquid crystal cells

We investigate the dependence of the relaxation time of the current flowing in a nematic cell submitted to an external dc voltage on the physical properties of the substrate. We show that previously presented analyses of the same problem are not very useful for practical applications. We compare our theoretical predictions with experimental data, and show that the agreement is rather good. The influence of the adsorption-desorption phenomenon on the relaxation time is also discussed.     

Dispersion analysis of the least‐squares finite‐element shallow‐water system

The frequency or dispersion relation for the least‐squares mixed formulation of the shallow‐water equations is analysed. We consider the use of different approximation spaces corresponding to co‐located and staggered meshes, respectively. The study includes the effect of Coriolis, and the dispersion properties are compared analytically and graphically with those of the mixed Galerkin formulation. Numerical solutions of a test problem to simulate slow Rossby modes illustrate the theoretical results. Copyright © 2003 John Wiley & Sons, Ltd.     

Kinetics of the reactions of the IO radical with dimethyl sulfide,methanethiol, ethylene,and propylene

The reactions of IO radicals with CH₃SCH₃, CH₃SH, C₂H₄, and C₃H₆ have been studied using the discharge flow method with direct detection of IO radicals by mass spectrometry. The absolute rate constants obtained at 298 K are the following: IO + CH₃SCH₃ → products (1): k₁ = (1.5 ± 0.2) × 10^?14; IO + CH₃SH → products (2): k₂ = (6.6 ± 1.3) × 10^?16; IO + C₂H₄ →products (3): k₃ < 2 × 10^?16; IO + C₃H₆ → products (4): k₄ < 2 × 10^?16 (units are cm³ molecule^?1 s^?1). CH₃S(O)CH₃ and HOI were found as products of reactions (1) and (2), respectively. The present lower value of k₁ compared to our previous determination is discussed.     

Nouveaux thiochlorures de molybdène(II): Mo6Cl10Y (Y = S,Se, Te): Structure et propriétés magnétiques et électriques

The thiochlorides Mo₆Cl₁₀Y (Y = S, Se, Te) have been prepared; they are isostructural with Nb₆I₁₁, space group Pccn, and have four formula units per unit cell. The X-ray structure of Mo₆Cl₁₀Se has been determined from three-dimensional single-crystal counter data and refined to a final R value of 0.053 for 3350 independent reflections. The most important result concerning this structure is a statistical distribution of the Se atom on the unit (Mo₆X′₈) with $\text{X′ ?}\text{7}\text{8}\text{Cl}\text{+}\text{1}\text{8}\text{Se}$: so the compound Mo₆Cl₁₀Se must be formulated $\text{(Mo}{}_6\text{Cl}{}_7\text{Se)Cl}{}_{\mathrm{<mtext>4</mtext><mtext>2</mtext>}}\text{Cl}{}_{\mathrm{<mtext>2</mtext><mtext>2</mtext>}}$. The diamagnetic and dielectric behavior of these new thiochlorides is discussed.     

Reactions de photoaddition de benzo[b]selenophenes avec l'acetylene dicarboxylate de methyle et avec le dichloro-1,2 ethylene

Photoirradiated in presence of acetophenone, benzo[b]selenophene and its 3-methyl derivative add to dimethyl acetylenedicarboxylate. In each ease, the primary reaction product is unstable and has not been isolated. Photoexeited in its triplet state (the energy of which is in the neighbourhood of 69 $\text{kcal}\text{mole}$) benzo[b]selenophene and its 2- and 3-methyl, 2,3 dimethyl, 3 acetoxy and 2-methyl-3-acetoxy derivatives add to 1,2 dichloroethylene leading to cyclobutanes. Neither cyclo-addition occurs in absence of photosensitiser. Single-crystal X-ray analysis gave the structures of the two adducts of 3-acetoxybenzo[b]selenophene with trans-1,2-dichloroethylene. In both compounds the chlorine atoms are trans.     

19F NMR chemical shifts of n-F-alkyl compounds

The examination of ¹⁹F chemical shifts for ca. 650 F-alkylated compounds of general formula CF₃(CF₂)_nCF₂X led to the following conclusions: the CF₂ groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF₂(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF₂(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds.