Determination of sulphide ion at trace levels by ethylation and gas chromatography

Summary A method is described for the determination of sulphide ion in aqueous samples by gas chromatography. Sulphide is ethylated with diethyl sulphate and the resulting diethyl sulphide is extracted with chloroform and determined with a gas chromatograph equipped with a flame ionization or a flame photometric detector. In the case of a flame photometric detector, the detection limit for sulphide ion is 0.05 g/ml. Other anions commonly found with sulphide ion do not interfere. Sulphide ion in spring waters was analysed by this new method and for comparison also by colorimetry (methylene blue). The results revealed the reliability of the new method.

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Bestimmung von Sulfidspuren durch Ethylierung und Gas-Chromatographie

Zusammenfassung Sulfid wird mit Diethylsulfat ethyliert, das gebildete Diethylsulfid mit Chloroform extrahiert und gaschromatographisch mit Hilfe eines Flammenionisationsoder eines flammenphotometrischen Detektors bestimmt. Die Nachweisgrenze beträgt 0,05 g S/ml für den FPD. Anionen, die üblicherweise mit Sulfid zusammen vorkommen, stören nicht. Das Verfahren wurde, im Vergleich mit der colorimetrischen Methylenblaumethode, auf Quellwasser angewendet. Es wurde gute Übereinstimmung der Ergebnisse erzielt.

     

Infrared-microwave double resonance of propynal by using the 3.51 μm HeXe laser

The 3.51 μm HeXe laser is magnetically tuned over a wavenumber of 0.2 cm^?1 and used for infrared absorption and double resonance spectroscopy. Eight rotation-vibration lines of propynal in the ν₂ band are assigned by the Stark effect. Eleven microwave transitions in the v₂ = 1 vibrational state are observed by the method of infrared-microwave double resonance. The rotational constants of the excited state and the band origin of the vibration ν₂ are determined from the observed spectra.     

Optically detected electron—nuclear double resonance and electron—nuclear—nuclear triple resonance study of 17O hyperfine coupling in the lowest nπ* triplet state of benzil

Optically detected ENDOR and electron—nuclear—nuclear triple resonance of ¹⁷O were measured via phosphorescence from ³(nπ^*) benzil in benzophenone-d₁₀ crystals at high magnetic field. The n and π^* spin densities on the oxygen atom are 0.201 and 0.092, respectively, the angle between the two CO bonds being 150°.     

Glueball mass estimate by strong coupling expansion in lattice gauge theories

In the formalism presented in the previous paper, the plaquette-plaquette correlation functions in arbitrary directions are calculated for Z(2), SU(2) and SU(3) up to order g^?8. Approximate restoration of rotational symmetry is observed in the continuum limit for SU(2), but much higher order corrections seem to be required in order to restore the symmetry for SU(3). The scalar glueball mass deduced from the plaquette-plaquette correlation function in the diagonal direction is 0.80 GeV, while the on-axis computation up to order g^?16 predicts it to be 0.64 GeV.     

The a-type rotational spectrum of isocyanic acid,HNCO, in the excited bending states

Rotational transitions of HNCO in the v₄ = 1, v₅ = 1, and v₆ = 1 vibrational states have been measured. The assignment of the a-type ^qR_K and ^qQ₁ branches has been made with the help of a qualitative discussion of the vibration-rotation interactions. Effective rotational and centrifugal distortion constants have been determined precisely for each vibrational K_a-rotational state, up to K_a = 4 for the lowest excited state and K_a = 3 for the other two excited states. The K_a dependence of the effective rotational constants B and D was observed to be quite anomalous for some of the transitions because of the a-type Coriolis interactions and accidental b-type Coriolis resonances. From a discussion of the selection rules and the effect on B and D of the interactions, the first excited state of the out-of-plane vibration, ν₆, has been assigned definitely to the second lowest excited vibrational state of HNCO.     

A digitally controlled diode-laser spectrometer: Infrared spectrum of the ν4 band of acetonitrile between 890 and 960 cm−1

The ν₄ vibration-rotation spectrum of acetonitrile (CH₃CN) has been measured using a newly constructed diode-laser spectrometer controlled digitally by a microprocessor. The spectrum was observed in the range between 890 and 960 cm^?1 with Doppler-limited resolution. The P and R branches of the ν₄ fundamental band have been assigned up to K = 9. A small anomaly found in the high K lines is being explained by an anharmonic resonance with the v₈ = 3³ state. The determined interaction constant is small, but significant.     

Persistent pi radical cations: self-association and its steric control in the condensed phase

Pi Radical cations, which are highly reactive in general, can be made persistently stable by appropriate structural modification with heteroatoms, pi-conjugated systems, and alkyl substituents. Many of these pi radical cations undergo self-association in the condensed phase. The steric control of such self-association of stabilized pi radical cations is the subject of the present article. Such an association can result in the formation of pi- and/or sigma-dimers. The pi-dimerization in particular is now considered as an important intermolecular interaction for model studies of a charge-transport phenomenon in positively doped conducting polymers. On the other hand, the intermolecular interactions can be suppressed when the pi-system is modified with sterically demanding structural units, for example, by annelation with bicycloalkene frameworks. This structural modification not only brings about unusual stabilization of the radical cations but provides valuable information on the electronic structure/properties of the positively charged pi-systems in a segregated state.     

Racemic but tropos (chirally flexible) BIPHEP ligands for Rh(I)-complexes: highly enantioselective ene-type cyclization of 1,6-enynes

[reaction: see text] The tropos (chirally flexible) or atropos (chirally rigid) nature of BIPHEP-Rh complexes at room temperature critically depends on the amines complexed. The aliphatic DPEN complex is atropos, whereas the aromatic DABN complex is tropos. BIPHEP-Rh chirality can thus be controlled by DABN at room temperature. The amine-free BIPHEP-Rh complex is tropos. At 5 degrees C, even amine-free BIPHEP-Rh complexes are atropos and hence can be used as enantiopure catalysts to give high enantioselectivity in ene-type cyclization of 1,6-enynes.     

Catalytic intermolecular Pauson-Khand-type reaction: strong directing effect of pyridylsilyl and pyrimidylsilyl groups and isolation of Ru complexes relevant to catalytic reaction

Some circumstantial evidence for the directing effect of the 2-pyridylsilyl group in the Ru-catalyzed intermolecular Pauson-Khand-type reaction (PKR) of alkenyl(2-pyridyl)silane, alkyne, and carbon monoxide has been provided. Most importantly, we have succeeded in isolating several monometallic Ru complexes relevant to the catalytic reaction: Ru(vinylsilane)(CO)(3) complexes and ruthenacyclopentene. While the stoichimetric reaction of the Ru(vinylsilane)(CO)(3) complex with an alkyne led to the formation of the corresponding cyclopentenone (PKR product) at 100 degrees C, the ruthenacyclopentene intermediate was quantitatively produced at 50 degrees C. This complex was also converted to a cyclopentenone upon heating at 100 degrees C. Moreover, it was also found that the Ru(vinylsilane)(CO)(3) complex and ruthenacyclopentene serve as catalysts in intermolecular PKR.