Interlaboratory studies of the determination of selected chlorobiphenyl congeners with capillary gas chromatography using splitless- and on-column injection techniques

The Community Bureau of Reference has organized a collaborative interlaboratory project to improve the analytical protocol for some specific chlorobiphenyls (CBs) within the European Community (EC). A series of test procedures were prescribed to optimize the gas chromatographic conditions for splitless and on-column injection, which substantially improved the quality of data. Important parameters included the initial column and injector temperatures and the choice of the polarity of the stationary phase. In a study with cleaned eel-fat extracts, coefficients of variation for reproducibility CV(R) ranging from 11 to 24% at the 0.04–0.3 mg/kg level per CB congener were obtained. No significant difference could be found between splitless- and on-column injection.     

Indium-based liquid clathrates. III. Inclusion compounds derived from [Bu4N][InCl3X] salts and their suitability as a catalysis medium

Tetrabutylammonium salts of the mixed haloindates, [Bu₄N][InCl₃X], X=Cl, Br, I, interact with aromatic solvents forming liquid inclusion compounds. The aromatic/cation ratio (A/C), a measure of the amount of guest aromatic, has been determined for a variety of simple aromatics. The values range from 2.6 to 0.4, substantially lower than the A/A of similar [Bu₄N][Al₂R₆X] liquid clathrates. The ability of these liquid clathrates to function as catalysis media has been explored. The solubility of (Ph₃P)₂Rh(CO)Cl and (Ph₃P)₃RhCl in the various clathrates was determined. It was found that significant leaching of the catalyst into the bulk aromatic solvent occurred, ranging from 13 to 94%. A related liquid clathrate, [Li·12-crown-4][InCl₄]·(C₆H₅CH₃)₂, had <1% of the dissolved catalyst leached.     

Absolute frequency measurements of the 0002-0000, 2001-0000, and 1201-0000 bands of N2O by heterodyne spectroscopy

The absolute frequencies of 39 lines in the 00⁰2-00⁰0, 20⁰1-00⁰0, and 12⁰1-00⁰0 bands of N₂O in the range 4300–4800 cm^?1 have been measured by heterodyne frequency techniques. The lines were each measured in Doppler-limited absorption, with a color-center laser as a tunable probe of the N₂O and two stabilized CO₂ lasers as reference frequencies. New rovibrational constants have been fitted to these measurements. Tables of calculated transition frequencies are given, with estimated absolute uncertainties as small as 10^?4 cm^?1. The pressure shifts of four lines have been measured, and the values fall within the range of 0 to ?2 MHz/kPa (0 to ?0.2 MHz/Torr).     

Optically stabilized tunable diode-laser system for saturation spectroscopy

We present an optically stabilized lead-salt diode-laser system which is the nucleus of a very-high-resolution instrument for sub-Doppler molecular spectroscopy in the mid-infrared. By application of external optical feedback, we have narrowed the diode-laser linewidth by two orders of magnitude, yielding a spectral width of less than 200 kHz. The diode- laser frequency is stabilized and controlled via the external reflector by variable-frequency offset-locking the diode-laser to a CO laser frequency. This substantial improvement in the spectral properties enabled us to perform a Lamb-dip experiment on a carbonyl sulfide (OCS) absorption line near 1985 cm^–1. We were able to detect a saturated dispersion signal at low pressure (5 Pa) with a signal-to-noise ratio of several thousand. The present paper describes the unique features of the optically stabilized tunable diode-laser system and its use as a spectroscopic tool for sub-Doppler applications.     

Solubility of dichlorotetraalkylpyridinecobalt III hexachlororhenate(IV) in water + methanol mixtures: Free energies of transfer of the complex cation from water into the mixtures

The solubility of salts [Co(3Rpy)₄Cl₂]₂]ReCl₆] has been determined in water + methanol mixtures. By comparing these with the solubilities of the salt Cs₂ReCl₆ and using calculated activity coefficients for the ions in the water+methanol mixtures, values for {G _t ^o (Co(3Rpy)₄Cl ₂ ⁺ )–G _t ^o (Cs⁺)} can be determined where G _t ^o is the standard Gibbs free energy of transfer from water to an aqueous mixture. G _t ^o (Cs⁺) from the solvent sorting scale and from the TPTB scale are then used to calculate G _t ^o (Co(3Rpy)₄Cl ₂ ⁺ ). These two sets of values for G _t ^o (Co(3Rpy)₄Cl ₂ ⁺ ) on the differing scales are then inserted into a free energy cycle applied to the bond extension Co(3Rpy)₄Cl ₂ ⁺ (initial state)Co(3Rpy)₄Cl²⁺+Cl^– (transition state) for the solvolysis in water and in water + methanol mixtures to produce values for G _t ^o (Co(3Rpy)₄Cl²⁺) using both scales. Data for the solubilites of [Copy₄Cl₂]₂[ReCl₆] and [Co(4Rpy)₄Cl₂]₂[ReCl₆] have been re-calculated to compare free energies of transfer for these complex cations with those specified above.