Comparison of four quantification methods for the determination of PCB in transformer oils

The analysis of PCB in transformer oils has been achieved with three HRGC/ECD based methods, proposed by the International Electrotechnical Commission (IEC/TC 10), by the Comité Européen de Normalisation (CEN/TC 19/WG 22) and by the Deutsches Institut für Normung (DIN 51 527). The same clean-up, described in the CEN/TC 19/WG 22, has been used for all the samples, allowing a comparison of the quantification procedure only. The total chlorine content has also been determined with X-ray fluorescence. These different methods of quantification are compared and their application for legislative purposes is discussed.Dedicated to Professor Dr Dieter Klockow on the occasion of his 60th birthday     

Structural changes in discotic samples during transition from crystal to discotic mesophase as revealed by electron microscopy and diffraction

Classical methods of structural analysis cannot be applied to liquid crystals because higher order reflections disappear during the transition from crystal to liquid crystal due to the reduction in long range orientational and translational correlations. However, in order to relate physical properties to the molecular architecture, it is essential to have information about molecular positions and orientations in the crystalline state as well as in the liquid crystalline state. In this work, the transition from crystalline to liquid crystalline phase is carefully monitored and the relationship between the original lattice and the new molecular positions found using electron diffraction. In addition to this, a new high resolution electron-microscopic technique is described in which the positions of molecules in the crystalline and the quenched discotic phase are directly imaged and the defects observed in the crystalline and LC phase compared and quantitatively analysed.     

Di[2-(4-substituted-phenyl)-3-mercapto-propenato]-nickel(II) complexes. Metallo-mesogens exhibiting broad nematic ranges

Di[2-(4-substituted-phenyl)-3-mercapto-propenato]-nickel(II) complexes have been synthesized and investigated. All of them are mesomorphic; they have nematic phases with wide ranges and typical Schlieren textures.     

Bioaccumulation and excretion of arsenic compounds by a marine unicellular alga,polyphysa peniculus

Polyphysa peniculus was grown in artificial seawater in the presence of arsenate, arsenite, monomethylarsonate and dimethylarsinic acid. The separation and identification of some of the arsenic species produced in the cells as well as in the growth medium were achieved by using hydride generation–gas chromatography–atomic absorption spectrometry methodology. Arsenite and dimethylarsinate were detected following incubation with arsenate. When the alga was treated with arsenite, dimethylarsinate was the major metabolite in the cells and in the growth medium; trace amounts of monomethylarsonate were also detected in the cells. With monomethylarsonate as a substrate, the metabolite is dimethylarsinate. Polyphysa peniculus did not metabolize dimethylarsinic acid when it was used as a substrate. Significant amounts of more complex arsenic species, such as arsenosungars, were not observed in the cells or medium on the evidence of flow injection–microwave digestion–hydride generation–atomic absorption spectrometry methodology. Transfer of the exposed cells to fresh medium caused release of most cell–associated arsenicals to the surrounding environment.     

Photoinduced electron transfer variables: rigidity or orientation?

The relatives photoreactives of bridged-ring systems 1, 3, 5-X and 6-X (X ≡ Cl or Br) have been studied at 254 nm in acetic acid. The formation of photosolvolysis product was rationalized in terms of photoinduced intramolecular electron transfer (ET) processes. The relative ease of ET in these donor—bridge—acceptor model system was analyzed in terms of known ET variables including free-energy changes, orientation effects and ridigity effects. The observed relative photoreactivities agreed better with the calculated free-energy changes when relative rigidities of the electron acceptor termini were evaluated. In general, the more rigid system were more photoreactive.     

Environmental plutonium: Reference states and alpha coefficients

The results of plutonium oxidation state distribution calculations do not depend on special attention to any oxidation state as has been incorrectly supposed in some literature sources. Experimentally determined alpha coefficients for natural water could make the distribution of environmental plutonium easy to estimate with a programmable pocket calculator.Mound is operated for the U.S. Department of Energy by EG&G Mound Applied Technologies, Inc., under Contract No. DE-AC04-88DP43495.     

Resonance ionization spectroscopy for trace analysis and fundamental research

Resonance ionization spectroscopy (RIS) and its combination with mass spectrometry (RIMS) have grown to become powerful techniques, which offer high sensitivity as well as elemental and isotopic selectivity. The principles of RIS and RIMS are introduced; they primarily concern the analysis of the optical spectra for the choice of efficient excitation schemes and the suitable design of the experimental apparatus. Recent applications span from studies of short-lived isotopes at on-line mass separators to a wide variety of trace analysis applications for radioactive isotopes, which can range from measurements of solar neutrino flux to environmental assessment.On leave from Pacific Northwest Laboratory, Richland, USA     

Comparison of short range interactions in nematic liquid crystals A 2H-NMR study of 5CB-d19 as a solute

Previous studies using dideuterium as a solute have demonstrated the importance for orientation of the interaction between the solute molecular quadrupole moment and the average electric field gradient present in liquid crystals. With the aim of learning about additional orientational mechanisms, we have studied the temperature dependence of the ²H-NMR spectra of the liquid crystal 5CB-d₁₉ as the solute in three liquid crystal mixtures: 55 wt % 1132/EBBA, 56·5 wt % 1132/EBBA and 70 wt % 5CB/EBBA. In these mixtures, the contribution from the environment to the average electric field gradient at the ²H nucleus of dideuterium is zero. The spectra of 5CB-d₁₉ in the mixtures 55 wt % 1132/EBBA and 56·5 wt % 1132/EBBA are equivalent, but are different from those in 70 wt % 5CB/EBBA. The spectra of 5CB in 55 wt % 1132/EBBA and 70 wt % 5CB/EBBA are analysed using two different models for the short range potential, and param eters of the models are used to compare the potentials in the different mixtures. For a given spectral splitting of the chain C₁ deuteron, the reduced short range potential is the same in all three mixtures studied. The spectral differences observed are a consequence of different nematic-isotropic phase transition temperatures combined with the effect of trans/gauche-isomerization in the hydrocarbon chain.