Phase equilibria in the ternary system PbO−P2O5−PbCl2

Journal of Thermal Analysis and Calorimetry - In the ternary system PbO?P2O5?PbCl2, the partial ternary system Pb5Cl2O4?Pb3Cl2O2?Pb10(PO4)6Cl2 was examined by thermal,...     

Über eine neue automatische Apparatur zur Zentigramm-Bestimmung von Kohlenstoff und Wasserstoff in organischen Substanzen

Zusammenfassung Das vom Verfasser undE. Sucharda schon 1928 angewandte Prinzip, die durch das Verhalten der Substanz beim Erhitzen bewirkten Druckschwankungen im Verbrennungsrohre zum Zwecke der automatischen Regulierung der Vergasungsgeschwindigkeit der Substanz bei der Elementaranalyse auszunutzen, wurde bei der Konstruktion einer neuen, elektrisch betriebenen, automatischen Apparatur angewandt. Hierbei wird das mit der Substanz gefüllte Mikroschiffchen mittels eines elektrischen Hochfrequenzgenerators erhitzt. Der Stromzufluß zu dem Hochfrequenzgenerator wird durch die erwähnten Druckschwankungen einoder ausgeschaltet. Die Verbrennung verläuft dann bei praktisch konstantem Druck im Verbrennungsrohre, also auch bei konstantem Sauerstoffüberschuß. Die neue Apparatur wird an Hand beigefügter Abbildungen beschrieben. Als Absorptionsmittel für Stickstoffoxyde werden 1 bis 2 g Bleidioxyd in einem 12 cm langen Porzellanschiffchen bei 190° angewandt. Die Absorption des Wassers erfolgt durch wasserfreies Kobaltchlorid, die der Kohlensäure ausschließlich durch Ascarit. Die Sauerstoffgeschwindigkeit im Verbrennungsrohre beträgt 8 ml pro Minute. Bei Substanzen, die mehr als 10% N enthalten, wird zwischen den Kohlensäureabsorptionsapparat und den Wasserabsorptionsapparat ein mit Mangandioxyd gefüllter Apparat eingeschaltet.

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Summary The principle used by the author andE. Sucharda as early as 1928, which employs the variations in pressure in the combustion tube resulting from the behavior of the substance when heated, for automatically regulating the rate of gasifying the substance was applied in the construction of a new electrically operated automatic apparatus. The micro boat charged with the sample is heated by means of a high frequency generator. The flow of current to the high frequency generator is switched on and off by the variations in pressure mentioned above. The combustion then proceeds at practically constant pressure in the combustion tube, and even when there is a constant excess of oxygen. The new apparatus is described in the accompanying figures. The nitrogen oxides are absorbed in 1 to 2 grams of lead dioxide contained in a porcelain boat (12 cm long) at 190°. The absorption of the water is by means of anhydrous cobalt chloride, while the carbon dioxide is taken up in ascarite. The speed of the oxygen in the combustion tube is 8 ml per minute. In the case of samples that contain more than 10% nitrogen, an apparatus filled with manganese dioxide is placed between the carbon dioxide absorber and the apparatus for taking up the water.

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Résumé Le principe de l'utilisation des variations de pression qui se produisent dans un tube à combustion en analyse élémentaire, lors du chauffage de la substance, a été utilisé dès 1928 par l'auteur etE. Sucharda pour la régulation automatique de la gazéification de cette substance. Il a été appliqué à la construction d'un nouvel appareil automatique commandé électriquement. La micronacelle qui contient la substance est chauffée électriquement à l'aide d'un générateur de courant de haute fréquence. Les variations de pression pendant la combustion provoquent l'ouverture ou la fermeture du circuit d'alimentation de ce générateur. Il en résulte que la combustion est effectuée à pression pratiquement constante ainsi qu'à excès d'oxygène constant. Ce nouvel appareil est décrit sur les figures de la publication.On utilise 1 à 2 grammes de bioxyde de plomb disposés dans une nacelle de porcelaine de 12 cm de longueur, portée à 190° pour absorber les oxydes de l'azote. L'eau est absorbée par du chlorure de cobalt anhydre et l'anhydride carbonique exclusivement par de l'ascarite. Le débit du courant d'oxygène dans le tube de combustion est de 8 ml par minute. Pour les substances contenant plus de 10% d'azote, on intercale un absorbeur à bioxyde de manganèse entre l'absorbeur à anhydride carbonique et l'absorbeur à eau.

     

A novel synthesis of racemic and enantiomeric forms of prostaglandin B1 methyl ester

3-(Dimethoxyphosphorylmethyl)cyclopent-2-enone was converted into (+/-)-prostaglandin B1 methyl ester in two steps involving regioselective alkylation at C(2) with methyl 7-iodoheptanoate and subsequent Horner-Wittig reaction with dimer of 2-hydroxyheptanal (42% overall yield). The use of (R)- and (S)-2-(tert-butyldimethylsilyloxy)heptanal for the Horner olefination reaction gave, after deprotection of the hydroxy group, the enantiopure forms of the title compound in 28% overall yield.     

Numerical method of non-isothermal curve analysis by means of electrical resistance measurement during cooling

The temperature-dependence of the electrical resistance of Al-Zn 78 wt.% was measured during linear cooling of the samples in the range of eutectoidal decomposition. The resulting resistancevs. temperature curves were analysed by:

deriving the temperature-dependence of the volume fractionx(T) of theη precipitate;

fitting the theoretical functionx(T)=x _h (T)+x _c (T) following from numerical integration of the reaction rate equations for the simultaneously occurring homogeneous (H) and cellular (C) precipitation processes.

As a result, the activation energiesE _h andE _c , the JMA exponentsn _h andn _c , the rate constantsk _h andk _c , and the critical temperaturesT _o of the two processes were estimated.     

Effect of Mobile Phase pH* on Chromatographic Behaviour in Chiral Ligand-Exchange Thin-Layer Chromatography (CLETLC) of Amino Acid Enantiomers

The enantiomers of some amino acids have been separated on commercial chiral TLC plates in reversed-phase mode. The effect of the pH* of the aqueous-organic mobile phase on the retention and mobility of the enantiomers and on selectivity was investigated. It was shown that for most of the amino acids investigated the highest enantioselectivity was obtained at pH* 3–4 or 6–7. The drift and disturbance of the baseline on the chromatograms were also much smaller at pH* 3–4 and 6–7.     

New 2+2, 3+3 and 4+4 macrocycles derived from 1,2-diaminocyclohexane and 2,6-diformylpyridine

Two new Schiff base macrocycles - a 4+4 condensation product and a meso-type 2+2 condensation product - were obtained in a reaction of trans-1,2-diaminocyclohexane and 2,6-diformylpyridine. Reduction of these compounds led to the corresponding 4+4 and 2+2 macrocyclic amines. The macrocycles were characterised by NMR spectroscopy and electrospray mass spectrometry. The symmetry and stereochemistry of these macrocycles, as well as of new 3+3 and 4+4 diastereomers identified in solution, has been established. X-Ray structures of the 2+2 and 4+4 Schiff base macrocycles confirm the configurations determined on the basis of spectroscopic investigations. The crystal structures reveal that the centres of the square-shaped 4+4 macrocycles form channels as a result of columnar stacking.     

The synthesis and the solvent and substituent effect on the spectroscopic characteristic of 3-ethyl-2-(p-substitued styryl)benzothiazolium iodides

The photophysical and photochemical properties of p-substitued 2-styryl-ethylbenzothiazolium iodides, possessing different electron-withdrawing or electron-donating groups are described. The dyes were prepared by the condensation of 3-ethyl-2-methylbenzothiazole salts with p-substituted benzaldehydes. The synthesis of suitable substrates is presented as well. We describe here the absorption, emission spectra and the luminescence quantum yield of hemicyanine dyes (SH) measured in 11 different organic solvents of varying polarity. Molecular structure of the synthesized dyes was established by (1)H NMR, electronic absorption and fluorescence spectrometry. The spectral data confirmed that all the compounds exist in E-configuration of their styryl residues. The planar molecular conformation is typical for the compounds with five-membered side aromatic moieties (for example benzothiazole). The compounds possessing N-alkyl substituent in phenyl ring, in contrast to the compounds with other substituents, exhibit low fluorescence quantum yield in THF solution. This indicates that for N-alkyl derivatives the non-radiative processes are much more effective than the radiative ones. The electronic absorption and fluorescence emission spectra of tested dyes demonstrate high sensitivity to the nature of substituent introduced into the aromatic ring.     

Polymerization of acrylonitrile by catalytic systems consisting of triphenylphosphine and a lewis acid

Polymerization of acrylonitrile in the presence of systems that consisted of triphenylphosphine (PPh₃) and a Lewis acid R_mMX_n (ZnCl₂, Me₃Al, Et₃Al, Et₂AlCl, EtAlCl₂, AlCl₃) was studied. The systems that contained Me₃Al and Et₃Al (i.e., Lewis acid of moderate acidity) were the most efficient catalysts. Conductometric measurements carried out in the polymerization systems showed the presence of ions. The presence of phosphonium cation in the polyacrylonitrile chain formed by the PPh₃–R_mMX_n catalytic systems was determined by IR, ¹H-NMR, and ³¹P-NMR spectroscopy. The average molecular weight measurements and kinetic chain lengths of polyacrylonitrile formed within the reaction time in the presence of PPh₃–Et₃Al showed that transfer reactions occur. According to the results obtained, the polymerization reaction of acrylonitrile by PPh₃–R_mMX_n involved a zwitterion formed by the attack of PPh₃ on acrylonitrile complexed by Lewis acid [Ph₃P^⊕? CH₂? C^?H? C?N → MR_mX_n] and the anion [CH₂?C^?? C?N] formed by the proton abstraction from the monomer.     

On the separation of nonadditive symmetric mixtures in nanoscopic slitlike pores: A simple model for racemic fluids

A grand canonical ensemble Monte Carlo simulation method is used to study the adsorption of nonadditive symmetric mixtures of Lennard-Jones spherical particles in nanoscopic slitlike pores. The walls of the pore are assumed to be formed by the parallel (100) planes of the model face centered cubic crystal of adjustable corrugation potential. It is demonstrated that depending on the nonadditivity effects in the mixture and the pore width the condensed phases formed inside the pore may have different structures. In particular, it is shown that the mixture may separate into layers containing only one component each and the stacking may depend on the pore width and properties of the mixture.     

pH gradient high-performance liquid chromatography: theory and applications

pH gradient high-performance liquid chromatography (HPLC) is a method of reversed-phase high-performance liquid chromatography suitable for ionogenic substances. It consists in programmed increase during the chromatographic process of the eluting strength of eluent with respect to the analytes separated. On the analogy of the conventional organic modifier gradient reversed-phase HPLC, in the pH gradient approach the eluting strength of the mobile phase increases due to its changing pH: increasing in case of acids or decreasing in case of bases. At the same time the content of organic modifier remains constant. A theory of the pH gradient HPLC has been elaborated. The resulting mathematical model is easily manageable. Its ability to predict changes in retention and separation of analytes following the changes in chromatographic conditions is demonstrated. The pH gradient method is uniquely suitable to determine pKa values of analytes. An equation is presented allowing to calculate pKa values basing on appropriate retention data. The effects on pKa are discussed of the concentration of methanol in the mobile phase. The RP HPLC-derived pKa data correlate to the reference pKa values (w(w)pKa) but are not identical. That may be explained by the effects on the chromatographically determined pKa of the specific interactions of analytes with stationary phases. The proposed pH gradient RP HPLC procedure offers a fast and convenient means to get comparable acidity parameters for larger series of compounds, like drug candidates, also when the analytes are available only in minute amounts and/or as complex mixtures.