Nature of intermediates in the synthesis of hydrocarbons from methanol

According to the GC-MS analysis of the composition of liquid hydrocarbons obtained in methanol conversion on ZSM-5 zeolites and the selectivity of cyclohexene conversion on these catalysts, the sequence of the aromatization reaction steps is discussed.

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-- , ZSM-5, .

     

Effect of NH3 and SO2 on n-butane oxidation

It has been established that NH₃ and SO₂ adsorption on the surface of V–P–O catalysts at reaction temperatures modifies its acid-base properties, which changes its activity and selectivity.

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, NH₃ SO₂ V–P–O -C₄H₁₀, - .

     

Dehydrogenation of methanol to formaldehyde over titanium alloys

The dehydrogenation of methanol to formaldehyde has been studied in the temperature range between 523 and 723 K over titanium alloys. The FeTi alloy showed a high selectivity for the formation of formaldehyde. Addition of zinc increased the specific rate of formaldehyde formation with a simultaneous decrease in its selectivity.

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523 723 K . FeTi . Zn .

     

Adaptation d'une methode d'analyse debitmetrique aux mesures sous pression de gaz carbonique. Application a l'etude de la reaction CdCO3 ⇄ CdO+CO2 jusqu'a 300 bar

Résumé Une méthode de mesure de débit de gaz associée à l'ATD est appliquée à l'étude de la réaction CdCO₃ CdO+CO₂. Après avoir présenté une adaptation du dispositif expérimental aux mesures sous pression de gaz carbonique et l'étalonnage correspondant, on donne les résultats obtenus jusqu'à 300 bar pour deux variétés de carbonate.

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A method based on the measurement of gas flow rate combined with DTA has been applied to the study of the reaction CdCO₃ CdO+CO₂. The construction of the experimental apparatus for the measurement of pressure and calibration are described, and results obtained with two different carbonates up to 300 bar are given.

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Zusammenfassung Eine auf Gasströmungsmessung beruhende Methode verbunden mit der DTA wurde zur Untersuchung der Reaktion CdCO₃ CdO+CO₂ herangezogen. Es wurde der Aufbau der Versuchseinrichtung zur Messung unter Druck und die Eichung beschrieben, sowie weiterhin die bis 300 bar mit zweierlei Karbonaten erhaltenen Versuchsergebnisse mitgeteilt.

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CdCO₃ CdO + ₂ , . . 300 .

     

Microthermogravimetric studies of the kinetics and thermodynamics of heterogeneous reactions in sulfur-containing atmospheres

A thermobalance for studies of the high-temperature sulfidation of metals and alloys is described. This apparatus permits the determination of mass changes in the sulfidized sample as functions of temperature and sulfur vapour pressure with an accuracy of 10^–6 g. Besides heterogeneous kinetics measurements, it has been shown that the chemical diffusion coefficients and deviations from stoichiometry of metal sulfides can also be studied as functions of temperature and sulfur pressure by means of equilibration measurements.

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Zusammenfassung Es wird eine Thermowaage zur Untersuchung der Hochtemperatur-Sulfidierung von Metallen und Legierungen beschrieben. Diese Apparatur ermöglicht die Bestimmung von MassenverÄnderungen der sulfidierten Proben in AbhÄngigkeit von der Temperatur und dem Schwefeldampfdruck mit einer Genauigkeit von 10^–6 g. Es wird gezeigt, da\ damit, sofern Gleichgewichtsmessungen ausgeführt werden, auch die chemischen Diffusionskoeffizienten und Abweichungen der Metallsulfide von der Stöchiometrie in AbhÄngigkeit von der Temperatur und dem Schwefeldampfdruck untersucht werden können.

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. 10^–6 . , , , .

     

Synthesis,spectral and electrochemical studies of alkoxo-bonded mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes incorporating tridentate ONO donor azophenolalcoholate/aldiminealcoholates

Mixed-ligand vanadyl(IV) and vanadyl(V) complexes with tridentate ONO donor azophenolalcoholate/aldiminealcoholates [viz., 2-hydroxy-2-hydroxymethyl-5-methylazobenzene (H₂L¹), N-(2-hydroxymethylphenyl)-salicylaldimine (H₂L²) and N-(2-hydroxymethylphenyl)1-hydroxy-2-naphthaldimine (H₂L³)] and bidentate NN [viz., 2,2-bipyridine (bipy) and 1,10-phenanthroline (phen)] or NO [viz., 8-hydroxyquinoline (Hhq)] donor ligands have been prepared and characterized by elemental analyses and by i.r., e.p.r. and u.v.–vis. spectroscopies. The data show that the vanadyl(IV) complexes exist in two isomeric solid forms viz., monomers and polymers, whereas vanadyl(V) complexes exist only in the monomeric form. The polymeric structure results from intermolecular V=OV=O interactions. The complexes with NN donor ligands are one electron paramagnetic and display two ligand-field transitions in the visible region, whereas the complexes with ON donor ligands are diamagnetic and exhibit only LMCT bands. The vanadyl(IV) complexes display an irreversible oxidation peak near +0.30 V for complexes with (L¹)^2– and near +0.55 V for complexes with (L²)^2– and (L³)^2– ligands, while the vanadyl(V) complexes display a quasi-reversible one electron reduction couple near –0.23 V versus s.c.e. The trends in the (V=O), values for the visible region transitions and the redox potential values for the vanadyl(IV) complexes have been scrutinized.     

Spectrophotometric Determination of Copper in Waste Water Using Liquid–Liquid Extraction in a Flow-Injection System

A flow-injection procedure for the determination of copper in waste water is described. The procedure is based on the formation of an ion-pair between tetrabutylammonium and the tetrathiocyanatocuprate(II) anion. This ion-pair is extracted with chloroform, and the absorbance of the organic phase is measured at 485nm. Concentrations of copper 0.4mg L^–1 can be detected with a linear application range of between 0.5 and 25mg L^–1, a relative standard deviation of 2.3% (0.8mg L^–1, n=10) and a sampling frequency of 30h^–1. Under the proposed working conditions, only Ni(II) and Pd(II) interfere at molar ratios Ni(II)/Cu(II) 50 and Pd(II)/Cu(II) 100.     

Some aspects of mathematical statistics as applied to nonisothermal kinetics

The suggested unified approach is based on the consideration of the entire set of kinetic functions as some space. The analysis of this space provides four classes of kinetic functions, characterized by similar properties and close values of kinetic parameters. The solution of the inverse kinetic problem within the unified approach reduces to finding unambiguously the class of kinetic functions.

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Zusammenfassung Die vorgeschlagene vereinheitlichte NÄherung geht davon aus, da\ das gesamte System der kinetischen Gleichungen als Raum angesehen wird. Die Analyse dieses Raumes ergibt vier Klassen von kinetischen Funktionen, die durch Ähnliche Eigenschaften und geschlossene Werte der kinetischen Parameter charakterisiert sind. Die Lösung des inversen kinetischen Problems reduziert sich in der vereinheitlichten NÄherung auf das eindeutige Auffinden der Klasse der kinetischen Funktionen.

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. , , , .

     

Alkaloids ofArundo donax. III. Reconsideration of the structures of donaxarine and donaxaridine

The alkaloid composition of the epigeal part of Arundo donax has been studied, and from an ether extract have been isolated the alkaloids donaxine, arundine, deoxyvasicinone, N-phenyl--naphthylamine, donaxarine, and donaxaridine. On the basis of an x-ray structural analysis, new structures have been established for donaxarine and donaxaridine:spiro[(N-methylpyrrolidin-2-one)-3,4-(2-methyl-3,1-benzoxazine)] and 3-hydroxy-3-(2-aminophenyl)-N-methyl-2 pyrrolidone, respectively. Spectral characteristics of the derivatives obtained are given and their chemical interconversions are described.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 720–727, September–October, 1995. Original article submitted March 22, 1995.     

Comparative thermogravimetric study of chlorinations of hematite and wustite

The reactions of hematite and wustite with Cl₂, COCl₂, CO+Cl₂ and gaseous CCl₄ were studied by thermogravimetry, X-ray diffraction and computer-assisted thermodynamic calculations. During the chlorination of hematite, only gaseous products were formed. The apparent activation energies were calculated from the isothermal TG curves. The chlorination of wustite involves the formation and transformation of a series of solid chloride products. FeCl₂(s), FeCl₃(s) and FeOCl(s) were found as intermediates during chlorination with Cl₂ or Cl₂+CO, while only FeCl₂(s) was detected in reactions with COCl₂ oe CCl₄. The chlorinations of the iron oxides with various agents were compared, and the differences in reactivity sequences were established.

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Zusammenfassung Die Reaktionen von HÄmatit und Wustit mit Cl₂, COCl₂, CO+Cl₂ and gasförmigen CCl₄ wurden thermogravimetrisch und röntgendiffraktometrisch untersucht. Thermodynamische Berechnungen wurden mit Computern ausgeführt. Bei der Chlorierung von HÄmatit entstehen nur gasförmige Reaktionsprodukte. Die scheinbaren Aktivierungsenergien wurden aus isothermen TG-Kurven berechnet. Bei der Chlorierung von Wustit wird eine Reihe von festen Chloriden gebildet. FeCl₂(s), FeCl₃(s) und FeOCl(s) treten bei der Chlorierung mit Cl₂ oder Cl₂ + CO als intermediÄre Produkte auf, wÄhrend bei Reaktionen mit COCl₂ oder CCl₄ nur FeCl₂(s) nachgewiesen wurde. Die verschiedenen Chlorierungsmittel wurden hinsichtlich ihrer Wirksamkeit miteinander verglichen und in einer entsprechenden Reihenfolge eingeordnet.

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Cl₂, COCl₂, CO+Cl₂ CCl_{2 4} , , . . . . Cl₂ Cl₂ + CO , FeCl₂, FeCl₃ FeOCl, COCl₂ CCl₄ — FeCl₂. .

     

Effect of water vapor upon thermal dehydration of Mg(H2PO4)2·2H2O

The dehydration of Mg(H₂PO₄)₂·2H₂O was investigated by means of thermal analysis, X-ray diffraction, IR absorption and chromatographic methods. The dehydration process and the structures of the products were found to depend considerably on the water vapor partial pressure in the gas phase. Therefore, in thermal analysis, the sample holder type had an analogous influence on the results. The dehydration end-product at 550 °C when the labyrinth crucible was used was well-crystallized Mg(PO₃)₂, whereas with the multiplate sample holder it was completely amorphous condensed magnesium phosphate.

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Zusammenfassung Mittels Thermoanalyse, Röntgendiffraktion, IR-Absorptionsspektroskopie und chromatografischen Methoden wurde die Dehydratation von Mg(H₂PO₄)₂·2H₂O untersucht. Es wurde festgestellt, daß der Dehydratationsvorgang und die Struktur der Produkte beträchtlich vom partiellen Dampfdruck von Wasser in der Gasphase abhängen. Der Probenhaltertyp in der Thermoanalyse besitzt deshalb einen analogen Einfluß auf die Ergebnisse. Wird ein Labyrinthtiegel verwendet, ist das Dehydratationsendprodukt bei 550 °C kristallines Mg(PO₃)₂, bei der Verwendung eines Mehrplattenprobenhalters hingegen erhält man amorph kondensiertes Magnesiumphosphat.

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Mg(H₂PO₄)₂·2H₂O , , - . , , , () . , 550 °C Mg(PO₃)₂, .

     

Kinetics of the oxidation of oxalic acid by cerium(IV) sulfate in dilute sulfuric acid

The kinetics of the oxidation of oxalic acid by cerium(IV) in sulfuric acid medium has been studied voltammetrically. The specific reaction rate is 132±4.0 M^–1s^–1 at 25.0 °C. The energy of activation is 62.6±3.0 kJ mol^–1. The entropy of activation is –2.7 J mol^–1K^–1. The specific reaction rate is influenced by complexation and also by ionic strength (). The most likely mechanism has been suggested.

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(IV) . 132±4,0 M^–1c^–1 25,0 °C. 62,6±3,0 ·M^–1. –2,7 ·K^–1M^–1. , (). .

     

Reactive properties of phosphine complexes of some transition metals in ethylene carbonylation

Catalystic properties of Group VIII transition metals and Cu, Ag, Au and Hg compounds in diethylketon synthesis from ethylene, carbon monoxide and hydrogen in concentrated aqueous solutions of trifluoroacetic acid containing triphenylphosphine have been examined in mild conditions (70°C, 1 bar). It has been established that under these conditions, in addition to Pd axcetate, a noticeable activity in diethylketone synthesis is observed only for Pt and Rh compounds.

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VIII , Cu, Ag, Au Hg , , , (70°C, 1 ). , Pd Pt Rh .

     

Solvent effect on reaction rates in molten salts

Predominant solvation of activated complex is shown to be characteristic for chemical and electrochemical reactions in molten salts.

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, .

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Presented at EUCHEM Conference on Molten Salts, September 2–8, 1990, Rio-Patras, Greece     

Some investigations on the photostabilization of polypropylene

The effect of substituted hydroxybenzophenone, benzotriazole and organic metal complexes on the photooxidation of PP films has been studied. It has been established that NiDBTC added in 1.0 wt. % is the most effective photostabilizer.While in the case of other stabilizers there is a slight increase in the Co content even during the induction period, with the application of NiDBTC practically no oxidation can be observed before the stabilizer completely disappears. This means that NiDBTC inhibits the photooxidation of the polymer even in low concentration.

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, - . , Ni, 1,0 . %. . , Ni , . , Ni .

     

Study of the evolution of a MoO3+Bi2MoO6 mixture in air and in the conditions of mild propene oxidation

MoO₃ can react with the gamma phase of bismuth molybdate (Bi₂MoO₆) in the conditions of propene oxidation to form the alpha phase (Bi₂Mo₃O₁₂) resulting in a more selective catalyst for propene oxidation to acrolein. Intimate contact between MoO₃ and the gamma phase is an important factor favoring the formation of the alpha phase.

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MoO₃ - (Bi₂MoO₆), - (Bi₂Mo₃O₁₂), .

     

On the thermal analysis of aliphatic carboxylic acids and their salts

The thermal behaviour of oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid, and of their mono- and disodium salts and calcium salts has been studied by derivatography. Some of the acids were distilled off without decomposition, while the others were decomposed in accordance with the rule of Blanc.Up to 600°, the decomposition of the monosodium salts consists of two principal steps. The first process is the liberation or the decomposition of the acid formed from the salt, the second step the decomposition of the normal salt into sodium carbonate and organic molecules. This decomposition mechanism was verified also by tracer technique on compounds labelled with the¹⁴C isotope. With most of the compounds unable to form ketones, the decomposition of the normal salt yields a great variety of organic compounds. In the case of adipates and pimelates the formation of cyclanones predominates.

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Zusammenfassung Es wurde das thermische Verhalten von Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Suberinsäure, Azelainsäure und Sebacinsäure, sowie ihrer Mono- und Dinatrium- und Calciumsalze derivatographisch untersucht. Einige dieser Säuren destillierten ohne Zersetzung, die übrigen zerlegten sich entsprechend dem Blancs'schen Gesetz.Die Zersetzung der Mononatriumsalze verlief bis 600° in zwei Stufen. In der ersten wurde die salzbildende Säure freigesetzt oder zersetzt, in der zweiten zersetzte sich das normale Salz in Natriumkarbonat und in organische Moleküle. Der Zersetzungsmechanismus wurde mit durch¹⁴C markierten Verbindungen kontrolliert. Bei der Zersetzung der normalen Salze und der Verbindungen, die unfähig sind Ketone zu bilden, entstehen mannigfaltige organische Verbindungen. Im Falle von Adipaten und Pimelinaten überwiegen Cyclanone.

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Résumé On a étudié par dérivatographie le comportement thermique des acides oxalique, malonique, succinique, glutarique, adipique, pimélique, subérique, azélaique et sébacique, et de leurs sels mono et disodiques et de calcium. Certains de ces acides distillent sans décomposition, alors que d'autres se décomposent suivant la loi de Blanc.La décomposition du sel monosodique se déroule en deux étapes jusqu'à 600°. Dans la première, l'acide formant le sel se dégage ou se désompose; dans la deuxième, le sel normal de sodium se décompose en donnant du carbonate de sodium et des molécules organiques. Le mécanisme de la décomposition a été vérifié à l'aide de combinaisons marquées par le¹⁴C.La décomposition des sels normaux et des combinaisons impropres à donner des cétones fournit une grand variété de composés organiques. Dans le cas des adipates et des pimélates, la formation de cyclanones prédomine.

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, , , , , - . , . 600° . , , — « » . , C¹⁴ . . .

     

ESR studies of molybdenum in Ti?Mo heteropoly acid supported on TiO2

ESR studies indicate that in Ti–Mo heteropoly acid supported on TiO₂, two types of Mo⁵⁺ ions are observed, corresponding to stabilization of the heteropoly blue with various degrees of interaction with the surface. , - TiO₂ Mo⁵⁺, .     

Determination of Volatile Sulfur Compounds in Beverage and Coffee Samples by Purge-and-Trap On-Line Coupling with a Gas Chromatography-Flame Photometric Detector

A sensitive and fast analytical method using purge-and-trap on-line coupling with gas chromatography was developed for the determination of trace volatile sulfur compounds including dimethyl sulfide (DMS), ethyl-methyl sulfide (EMS), and dimethyl disulfide (DMDS) in beverage and coffee samples. The analytes were purged for 12min from the sample by high purity nitrogen at a flow rate of 35KPa and preconcentrated in the cooled fused-silica capillary trap at –75°C. The NaCl content in the samples was maintained at 10%. The volatile sulfur compounds were separated with an Agilent-6890 gas chromatograph by a suitable temperature program and detected by means of a flame photometric detector (FPD). The detection limits were 80ngL^–1 for DMS, 80ngL^–1 for EMS, and 100ngL^–1 for DMDS, respectively. This method was successfully applied to the determination of volatile sulfur compounds in different beverage and coffee samples.     

Kinetics of the homogeneous oxidation of hydrogen by platinum(II) and platinum(IV) chloro complexes in aqueous solution

The kinetics of the homogeneous oxidation of hydrogen in the Pt(II)–Pt(IV)–Cl^––H₂O system has been studied for the first time in conditions permitting to avoid the formation of Pt-black. It is shown that platinum (II) [Pt(II)Cl_i(H₂O)_4-i, where i=1, 2, 2], is active in the reaction, whereas the PtCl ₄ ^2– complex and platinum(IV) do not react with hydrogen.

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, Pt-, H₂ Pt^II–Pt^IV–Cl^––H₂O. (II) (Pt^IICl_i(H₂O)_4-i, i=1, 2, 3); PtCl ₄ ^2– (IV) .