13C NMR study of polarizations and polarization ranges of vinylene groups in seven series of related compounds

Polarizations, polarization ranges and ratios of polarization ranges for vinylene groups in seven series, namely chalcone derivatives, ferrocene analogues of chalcone, stilbene derivatives, ferrocene analogues of stilbene, and styrene derivatives, were studied. The polarization ranges spanning the intervals between ¹³C NMR chemical shifts of the derivatives substituted by p-NO₂ and p-NMe₂ groups are compared in these related compounds. The influence of the side-chain groups in the vinylene moiety and of the sign of the polarization on the substituent-effect are discussed.     

The Ru(dipy)32+-Bromate-Malonic acid oscillating system

The Ru(dipy) ₃ ²⁺ -bromate-malonic acid oscillating system was in vestigated. It has been established that at early stages of the reaction the period of oscillation is about 20 sec and the potential change is about 170 mV; chloride at concentrations hiherg than 10^–3M is an inhibitor. The rates of both heat evolution and formation of bromomalonic acid are periodic. The activation energy of the oscillating (E) is 16.2 kcal mol^–1. Ru(dipy) ₃ ²⁺ -- . , 20 , 170 ; , - 10^–3 M, . . (E) 16,2 /.     

Novel electroanalytical techniques for pollution analysis

Summary Two new analytical techniques are described. The so-called injection technique operates on evaluating a dynamic concentration signal as a result of following the concentration change in a certain part of a flow-through channel after injecting a sample or reagent at a small volume into the current of an appropriate solution flowing at a constant rate.The second technique, the programmed coulometric titration technique, also uses the flow-through channel principle; that means this novel technique allows the more precise titrimetric way of analysis in flowing solutions. In the case of both techniques potentiometric and voltammetric detectors were involved. Several examples proved the multifold advantages of these techniques for environmental analysis.

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Neue elektroanalytische Verfahren für die Umweltanalyse

Zusammenfassung Zwei neue Methoden werden beschrieben. Die sog. Injektionstechnik wertet ein dynamisches Konzentrationssignal aus, das sich aus der Änderung in einem Durchflußkanal ergibt, wenn Probe oder Reagens in kleinen Volumina in einen konstant fließenden Flüssigstrom injiziert werden. Das zweite Verfahren, die programmierte coulometrische Titration, erlaubt die Anwendung der genaueren titrimetrischen Technik auf fließende Lösungen. Bei beiden Methoden werden potentiometrische und voltammetrische Detektoren verwendet. Mehrere Beispiele zeigen die vielfachen Vorteile dieser Verfahren bei der Anwendung auf die Analyse von Umweltmaterial.

Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria     

Role of rhenium in bimetallic reforming catalysts

The influence of rhenium on the behavior of a Pt/Al₂O₃ catalyst was studied in n-hexane reaction by means of dilution of the catalyst bed with Re/Al₂O₃. Parallel to activity, selectivity and ageing data obtained in slug pulse and continuous flow reactors, the amount of the surface carbon formed during the reaction was determined and its reactivity in hydrogen atmosphere was also studied. It is suggested that in the presence of rhenium due to the increase in the amount of hydrogen available for hydrogen consuming reactions including hydrodepolymerization of the carbonaceous surface overlayer, the routes of ageing processes are changed, resulting in lower carbon content on the catalyst and less pronounced catalyst deactivation.

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Pt/Al₂O₃ -, Re/Al₂O₃. , , , , . , , , , , , , .

     

Formation and stability of N-heterocyclic carbenes in water: the carbon acid pKa of imidazolium cations in aqueous solution

We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes.     

Selective liquid adsorption and structural properties of montmorillonite and its hexadecylpyridinium derivatives

Summary An X-ray diffraction method was used to study the structures of montmorillonites, the surfaces of which were covered to a systematically increasing extent with hexadecylpyridinium (HDP) cations. It was found that, depending on the degree of cover of the surface, the HDP cations form a mono- or bimolecular layer in the interlayer space. A detailed investigation was made of the selective sorption of binary mixtures on montmorillonite and on HDP-montmorillonites with different surface coverages. The adsorption excess isotherms were determined, as were the adsorption capacities from analysis of the isotherms, and also the equivalent specific surface areas.It was established that from benzene-n-heptane mixtures the benzene is adsorbed only on the external surface of montmorillonite, while in the case of organocomplexes it causes moderate disaggregation.From benzene, alcohols with different numbers of carbon atoms are also preferentially adsorbed on the internal surfaces of montmorillonite; with the rise in the number of carbon atoms, the extent of interlamellar adsorption decreases. In the case of HDP-montmorillonites in methanol-benzene mixtures, the adsorption capacity exhibits a monotonous increase with the degree of organopbility in the range under consideration. In the event of optimum organophility the disaggregation of the organocomplex is complete, and the equivalent specific surface area is 764-778 m² · g^–1. The swelling of the organocomplex, which can be characterized by X-ray diffraction measurement, is in close correlation with the interlamellar liquid adsorption. The results show modification of the surface of montmorillonite with HDP cations fundamentally determines the nature and extent of the selective liquid adsorption.

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Zusammenfassung Die Struktur von mit Hexadecyl-pyridinium(HDP)-Kationen im systematisch gesteigerten Maße bedeckten Montmorilloniten wurde mit der Röntgendiffraktions-Methode untersucht. Es wurde festgestellt, daß die HDP-Kationen, von der Bedeckung der Oberfläche abhängend, im Schichtzwischenraum eine mono- bzw. bimolekulare Schicht bilden. Die selektive Sorption binärer Gemische wurde an Montmorilloniten und an HDP-Montmorilloniten verschiedener Bedeckung eingehend untersucht. Es wurden die Adsorptionsisothermen von Flüssigkeitsgemischen und aus deren Analyse die Adsorptionskapazitäten und die äquivalenten spezifischen Oberflächen bestimmt.Es wurde festgestellt, daß aus Benzol-n-Heptan-Gemischen das Benzol nur an der äußeren Montmorillonite-Oberfläche adsorbiert wird, während es bei Organokomplexen eine mäßige Desaggregation verursacht. Die Adsorption von Alkoholen verschiedener Kohlenstoffzahl aus Benzol erscheint auch an inneren Montmorillonit-Oberflächen bevorzugt; mit zunehmender Kohlenstoffzahl nimmt das Ausmaß der interlamellaren Adsorption ab. Bei HDP-Montmorilloniten zeigt die Adsorptionskapazität aus Methanol-Benzol-Gemischen mit zunehmender Organophilität im untersuchten Gebiet eine monotone Steigerung. Im Falle optimaler Organophilität ist die Desaggregation vollständig, die äquivalente spezifische Oberfläche beträgt 764-778 m²/g. Die durch Röntgenn-diffraktionsmessung charakterisierbare Quellung des Organokomplexes steht mit der interlamellaren Flüssig-keitsadsorption in engern Zusammenhang. Unsere Ergebnisse zeigen, daß Charakter und Ausmaß der selektiven Flüssigkeitsadsorption durch die Modifizierung der Montmorillonit-Oberfläche mit HDP-Kationen grundlegend verändert wird.

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With 14 figures and 4 tables     

Coloring linear hypergraphs: the Erdős–Faber–Lovász conjecture and the Combinatorial Nullstellensatz

Designs, Codes and Cryptography - The long-standing Erdős–Faber–Lovász conjecture states that every n-uniform linear hypergaph with n edges has a proper vertex-coloring using...     

Permutation functions and (n,m)-commutativity of semigroups

By [4], a semigroupS is called an (n, m)-commutative semigroup (n, m ∈ ?⁺, the set of all positive integers) if $$x_1 x_2 \cdot \cdot \cdot x_n y_1 y_2 \cdot \cdot \cdot y_m = y_1 y_2 \cdot \cdot \cdot y_m x_1 x_2 \cdot \cdot \cdot x_n $$ holds for allx ₁,...,x _n ,y ₁,...,y _m ∈S It is evident that ifS is an (n, m)-commutative semigroup then it is (n′,m′)-commutative for alln′≥n andm′≥m. In this paper, for an arbitrary semigroupS, we determine all pairs (n, m) of positive integersn andm for which the semigroupS is (n, m)-commutative. In our investigation a special type of function mapping ?⁺ into itself plays an important role. These functions which are defined and discussed here will be called permutation functions.     

On the Haar measure of the quantumSU(N) group

We prove that the Haar state associated to the compact matrix quantum groupSU (N) is faithful for ]–1,1[,0, and anyN2.