On similarity of hydrogen-bonded networks in liquid formamide and water as revealed in the static dielectric studies

The paper presents the experimental verification of the result obtained with the molecular dynamics simulation which revealed the differences in the topology of the hydrogen-bonded networks in liquid formamide and water, namely, the differences in their intermolecular cyclization process (I. Bakó, et al. J. Chem. Phys. 2010, 132, 014506). It is shown in our paper that the difference in the (simulated) size distribution of the hydrogen-bonded molecular rings in water (a relatively sharp maximum at about 6 molecules) and formamide (a broad maximum at about 11 molecules) strongly manifests itself in the experimental values of the Kirkwood correlation factor of the compounds. A much larger number of molecules included in the cyclic species (of more or less compensated dipole moment) leads to significant decrease of the Kirkwood correlation factor of formamide in comparison to that of water. Besides, as a consequence of an enhancement in formation of the cyclic multimers of formamide, one observes an essential reduction of the orientational entropy increment of that liquid, in comparison to the entropy effect related to liquid amides where the chain multimers are formed.     

Untersuchungen über Radium- und Bariumfällungen unter Anwendung von Thorium X als Indikator

Zusammenfassung Zunächst wird im Zusammenhang mit Messungen der Fällungsgeschwindigkeit von Thorium X in sulfathaltigen Lösungen eine Methode beschrieben, die es gestattet, während der Fällung, und zwar ohne Störung des Fällungsvorganges, diejenigen Mengen von Thorium X zu bestimmen, die sich jeweils zu bestimmten Zeitpunkten noch in Lösung befinden; dabei konnte der Gehalt an Th X mit Hilfe einer Emanationsmethode genau ermittelt werden.Die Versuchsergebnisse, die in Kurven wiedergegeben sind, lassen deutlich erkennen, daß die Fällung von Th X nicht momentan erfolgt, sondern eine gewisse Zeit beansprucht, die von der Konzentration der zugesetzten Sulfat- und Bariumchloridlösung sowie vom Zusatz anderer Fremdionen abhängig ist; es wird jedoch schließlich immer der gleiche Endzustand vollständiger Ausfällung erreicht, wenn mit äquivalenten Mengen gearbeitet wird.Die Annahme, daß die Fällung momentan erfolgt, daß aber das Fällungsprodukt sich im Laufe der Zeit von einem feinkristallinischen Zustand mit großer Emanierfähigkeit in einen grobkristallinen mit geringer Emanationsabgabe umwandelt, konnte durch besondere Experimente widerlegt werden.Schließlich wird noch eine Apparatur zur Messung des Thorongehalts angegeben, die auch für Untersuchungen des Thoriumgehalts von Quellwässern Anwendung finden kann.

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Summary A method has been worked out which makes it possible to determine the rate of precipitation of thorium X in solutions containing sulphate ion. The amount of thorium X is determined rapidly and accurately by the thorium emanation—thoron—evolved under fixed conditions. Determinations have been made every 5 minute during the time following precipitation, and the results are given graphically.They bring forward, very clearly, that the precipitation of thorium X requires a certain length of time, depending on the concentration of the sulphate and barium-chloride solutions used and on the presence of other ions. However, if equivalent quantities of barium- and sulphate ions are used, the same final result is always reached.It might have been supposed that the precipitation takes place instantaneously but that in course of time, the precipitate undergoes changes through recrystallisations and that the emanating power changes accordingly. That hypothesis, however, could be disproved by special experiments.At last an apparatus for measuring the thoron content is given which can also be applied for investigations of the thorium content of source waters.

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Résumé Les auteurs décrivent une méthode qui leur a permis de déterminer la vitesse de précipitation du thorium X en solutions contenant de l'ion sulfurique. Le thorium X est dosé par son émanation — le thoron — sous des conditions fixées, et les dosages peuvent se faire à intervalles régulières pendant le temps que demande la précipitation.Les résultats montrent que la précipitation du thorium X ne se fait point à l'instant, mais demande un certain temps, dépendant de la concentration des solutions de sulfate et de chlorure de baryum ajoutées et aussi de la présence d'ions étrangers.Les auteurs réfutent par leurs expériences la théorie que la précipitation se fait momentanément et que le précipité change peu à peu son état cristallin et par cela même, sa faculté de dégager l'émanation.Enfin les auteurs décrivent un appareil pour les dosages de thoron, qui pourra servir de même pour déterminer la teneur en thorium dans les eaux vives.

     

Pressurised hot-water extraction of brominated flame retardants in sediment samples

Summary A pressurised, hot-water extraction (PHWE) method was developed for brominated flame-retardants in sediments. The effect of extraction time, temperature and pressure on PHWE recovery was investigated, together with solid-phase collection parameters (trapping material, length of trapping column, eluent composition). The concentrated extracts were analysed by GC-MS. PHWE recoveries were compared with those obtained by conventional Soxhlet-extraction. In general, recoveries were much higher with PHWE than with Soxhlet.     

Dielectric studies of nematic-smectic A-reentrant nematic transition in the 8OCB/6OCB mixtures

The results of measurement of the anisotropies of the electric permittivity and conductivity for pure 8OCB and 6OCB together with their mixtures are presented. It was found that (i) the dielectric properties of mesophases composed of molecules with a strong tendency to antiparallel association in the nematic phase (8OCB) and molecules which do not exhibit such a tendency (6OCB) undergo a drastic change in mixtures with a relatively low concentration of 6OCB, (ii) the effect of smectic density modulation in the N-S_A-N_R sequence is very subtle, and (iii) for concentrations higher than a critical value the nematic phase exhibits a smectic-like ordering which vanishes with increasing concentration of 6OCB.     

Dielectric polarization and non-linear dielectric effects in pivalonitrile solutions

Dielectric polarization and non-linear dielectric studies of solutions of pivalonitrile (CH₃)₃CN in carbon tetrachloride, cylohexane and n-hexane are presented. The contributions of Langevin orientation, dipolar coupling and pretransitional fluctuations have been separated from the observed dielectric non-linear effect.     

Dielectric and orientational properties of nematogenic 4-<Emphasis Type="Italic">n</Emphasis>-octyl(4′-cyanophenyl)benzoate

Experimental studies of the dielectric properties in the nematic and isotropic phases of 4-cyanophenyl-4′-n-octylbenzoate (8CPB) have been performed in the frequency range from 50 kHz to 100 MHz. The relaxation process related to the rotation around the short molecular axis has been analysed. The results obtained have revealed that in the vicinity of the I-N phase transition, the molecular subdiffusional rotation process occurs. It is connected with the pretransitional effects which are observed both in the static and dynamic dielectric measurements. On the basis of the temperature dependence of the relaxation time in the nematic and isotropic phases, the orientational order parameter 〈P₂〉 has been determined. The values of 〈P₂〉 obtained in this way have been compared with those evaluated from the measurements of the polarized electronic absorption of the dichroic dye, dissolved as guest probe in the mesogenic host.     

Static and dynamic dielectric effects in the vicinity of the isotropic to nematic phase transition in 7CB

Static and dynamic dielectric measurements were performed with very high accuracy on a mesogenic compound n‐heptylcyanobiphenyl (7CB) in the isotropic (I) and nematic (N) phases. The critical‐like temperature behaviour of the static permittivity of isotropic 7CB in the vicinity of the I–N phase transition can be described with the critical exponent close to 0.5, indicating the tricritical nature of the transition. Anomalously slow rotational diffusion (subdiffusion), characterized by a fractal value of the diffusion exponent α, is observed in the vicinity of the I–N transition with a lambda‐like profile of the exponent temperature dependence.     

Non-linear dielectric studies of the isotropic-smectic phase transition in 6-DBT and 7-DBT

Results are reported for measurements of Δε/E₂ for 6-DBT and 7-DBT (5-trans-n-alkyl-2(4'-isothiocyanianophenylo)-1,3-dioxane, n = 6, 7) in the isotropic phase, in the vicinity of T_SA1, and for 6-DBT solutions in dioxane over a broad range of temperatures. In the immediate vicinity of T_SA1 divcrgence from the Landau-de Gennes model was observed. From measurements made in solutions of 6-DBT in dioxane it was concluded that the antiparallel orientation of dipoles is preferred.     

Fractional Stokes-Einstein-Debye relation and orientational entropy effects in strongly hydrogen-bonded liquid amides

The impedance spectroscopy studies performed for two strongly hydrogen-bonded liquid amides: N-methylpropionamide (NMP, CH(3)·NH·CO·C(2)H(5)) and N-ethylacetamide (NEA, C(2)H(5)·NH·CO·CH(3)) have shown that the two centers of the peptide linkage, -NH·CO-, active in the C=OH-N hydrogen bonds formation, exhibit quite different sensibilities to the steric screening effects. In contrast to the oxygen atom, a relatively small change (CH(3)- to C(2)H(5)-) in the screening of the hydrogen atom leads to an essential decrease of the degree of the amide self-association. As a consequence, both the static dielectric permittivity and the orientational entropy increment of NEA are essentially lower than those of NMP. However, it was found that the dynamic processes studied are only weakly influenced (in the case of dc conductivity, σ(DC)) or totally not influenced (the dielectric relaxation time, τ(D)) by the different degrees of NMP and NEA self-association. The experiment shows that for both the amides, the logσ(DC) vs. logτ(D) dependence is nonlinear and can be described with the fractional Stokes-Einstein-Debye relation, σ(DC)τ ? const, with the exponent s varying from about -0.8 to about -0.6 in the temperature range from 5 °C to 110 °C.