Zur quantitativen Spectral-Analyse

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Rate constants for the gas‐phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250–430 K

The rate constants k₁ for the reaction of CF₃CF₂CF₂CF₂CF₂CHF₂ with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm³ reaction chamber with either CHF₂Cl or CH₂FCF₃ as a reference compound. OH radicals were produced by UV photolysis of an O₃–H₂O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k₁ (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (FP‐LIF method) and (1.72 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (LP‐LIF method), whereas the K₁ (298 K) values determined by the relative method were (1.87 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CHF₂Cl reference) and (2.12 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CH₂FCF₃ reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K₁ = (4.71 ± 0.94) × 10^?13 exp[?(1630 ± 80)/T] cm³ molecule^?1 s^?1. Using kinetic data for the reaction of tropospheric CH₃CCl₃ with OH radicals [k₁ (272 K) = 6.0 × 10^?15 cm³ molecule^?1 s^?1, tropospheric lifetime of CH₃CCl₃ = 6.0 years], we estimated the tropospheric lifetime of CF₃CF₂CF₂CF₂CF₂CHF₂ through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004     

Naphthyl azomesogens with lateral chloro groups

A homologous series of azomesogens, 2″-[4-(4′-n-alkoxybenzoyloxy)-2-chlorophenylazo] naphthalenes, with lateral chloro groups was synthesised. All the homologues synthesized exhibit enantiotropic nematic mesophase. The mesomorphic properties of the present series are compared with other structurally related series to evaluate the effect of lateral chloro group and its position on mesomorphism This paper was presented at the 10th National Conference on Liquid Crystals held at Bangalore, India during 9–11 October 2003.     

New Weyl groups forA 1 (1) and characters of singular highest weight modules

We consider singular Verma modules overA ₁ ⁽¹⁾ , i.e., Verma modules for which the central charge is equal to minus the dual Coxeter number. We calculate the characters of certain factor modules of these Verma modules. In one class of cases we are able to prove that these factor modules are actually the irreducible highest modules for those highest weights. We introduce new Weyl groups which are infinitely generated abelian groups and are proper subgroups or isomorphic between themselves. Using these Weyl groups we can rewrite the character formulae obtained in the paper in the form of the classical Weyl character formula for the finite-dimensional irreducible representations of semisimple Lie algebras (respectively Weyl-Kac character formula for the integrable highest weight modules over affine Kac-Moody algebras) so that the new Weyl groups play the role of the usual Weyl group (respectively affine Weyl group).     

New FIR laser lines and frequency measurements for optically pumped CD3OH

Twenty new cw FIR laser lines in CD₃OH, optically pumped by a CO₂ laser, are reported. The frequencies of 39 of the stronger laser lines were measured relative to stabilized CO₂ lasers with a fractional uncertainty, as determined by the reproducibility of the FIR frequency itself, of 2 parts in 10⁷.Contribution of the U.S. Government, not subject to copyright.