Study of selective dissociation in C6F5H?C6F5D mixtures induced by intense CO2 laser pulses

Irradiation of a C₆F₅H–C₆F₅D mixture at 1 Torr by a tunable CO₂ pulse laser brings about chiefly dissociation of one component depending on the frequency of emission absorbed by the proper molecules. The addition of radical acceptors increases the selectivity by suppressing secondary reactions.

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C₆F₅H C₆F₅D 1 CO₂-, , . .

     

Transverse photothermal deflection spectroscopy (PDS) applied to thermal diffusiyity measurements

Transverse photothermal deflection spectroscopy(PDS) is applied for the determination of thermal diffusivities of solid surfaces. The theory of PDS is briefly recalled and some approximated analytical formulae concerning the transverse configuration are derived. In materials where the thermal diffusivity is smaller than that of the air, the dependence of the deflection angle on the displacement between pump and probe beams is shown to have a minimum that relates to the thermal diffusivity, thereby allowing its straightforward measurement. Measurements carried out on Al₂O₃ samples with different porosities at room temperature show a good agreement between experiment and theory.

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Zusammenfassung Die transverse photothermische Reflektionsspektroskopie (PDS) wird zur Bestimmung der thermischen Diffusivität von festen Oberflächen herangezogen. Die Theorie der PDS wird kurz dargelegt und einige sich auf die transverse Konfiguration beziehenden analytischen Näherungsgleichungen abgeleitet. Es wird gezeigt, daß bei Materialien mit kleinerer thermischer Diffusivität als Luft die Abhängigkeit des Deflektionswinkels von der Ablenkung zwischen Pumpen- und Probenstrahl ein Minimum aufweist, das mit der thermischen Diffusivität im Zusammenhang steht und somit deren zuverlässige Messung ermöglicht. An Al₂O₃-Proben unterschiedlicher Porosität bei Raumtemperatur ausgeführte Messungen zeigen gute Übereinstimmung von Experiment und Theorie.

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. , . , , , , . , , .

     

Supercooling phenomena in the binary systems: Acetamide-electrolytes

This paper presents a final discussion on studies of solutions of electrolytes in molten acetamide. These studies deal with cryoscopic and ultrasonic (by shear waves) techniques and reveal the complexity of the behaviour of these systems due to strong ion-solvent interactions.

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Zusammenfassung Die über Lösungen von Elektrolyten in geschmolzenem Acetamid ausgeführten Untersuchungen werden diskutiert. Diese Untersuchungen erstrecken sich auf kryoskopische und Ultraschall-Methoden und vermitteln ein Bild von der durch starke Ionen-Lösungsmittel-Wechselwirkungen bedingten Komplexität des Verhaltens dieser Systeme.

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. , - - .

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Thanks are due to CNR and MPI (Rome) for financial support, and to R. Borgarucci for technical assistance.     

Modification of Fe species in FeNaY zeolite by NaCl treatment

The treatment of Fe(III)NaY zeolite with NaCl solution does not lead to a back-exchange of ferric species but the cationic Fe rearranges into new complexes which are more deeply reduced by hydrogen and less self-reduced by vacuum heat treatment than the parent Fe species in FeNaY zeolite.

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Fe(III)NaY NaCl . , Fe , , , Fe FeNaY.

     

Structure of Pt/ZnAl2O4 catalysts

The effect of the support preparation technique (solgel and coprecipitation) on the final Pt/ZnAl₂O₄ catalyst is presented. The structural properties of the solids obtained are correlated to the selectivity and activity for isobutane dehydrogenation in H₂ and He reaction media. If a highly dispersed catalyst is suitable, the support has to be prepared by the sol-gel method.

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( — ) Pt/ZnAl₂O₄. H₂ He. , — .

     

Double crystallization of biaxially oriented polypropylene

The melting conditions of biaxially oriented polypropylene (BOPP) have a very strong effect on the courses of both non-isothermal and isothermal crystallization from the melt. It has been shown that the crystallization proceeds by two mechanisms. Depending on the melting conditions, both crystallization mechanisms can proceed individually or simultaneously (double crystallization). The high rate mechanism, occurring in non-isothermal crystallization at low undercooling and observed in isothermal crystallization, can be attributed to the ordered structure of the melt preserved after melting, presumably a mesomorphic state. The second component corresponds to crystallization from the isotropic melt.Anomalous crystallization of BOPP samples can be eliminated by energetic heat treatment, by the destruction of ordered structures. As a result of this treatment, the characteristics of crystallization and its quantitative parameters will become similar to those of unoriented polypropylene.

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Zusammenfassung Die Schmelzbedingungen haben bei biaxial orientierten Polypropylenen (BOPP) eine sehr starke Wirkung auf den Verlauf der sowohl nichtisothermen als auch der isothermen Kristallisation aus der Schmelze. Es wurde gezeigt, daß die Kristallisation nach zwei Mechanismen verläuft. In Abhängigkeit von den Schmelzbedingungen können beide Kristallisationsmechamismen einzeln oder simultan verlaufen (doppelte Kristallisation). Der Hochgeschwindigkeitsmechanismus, der bei der nichtisothermen Kristallisation bei geringer Unterkühlung auftritt und bei der isothermen Kristallisation beobachtet wird, kann der geordneten Struktur der Schmelze zugeschrieben werden, welche nach dem Schmelzen bis zu einem mesomorphen Zustand erhalten bleibt. Die zweite Komponente entspricht der Kristallisation aus isotroper Schmelze.Die anomale Kristallisation der BOPP-Proben kann durch energische Hitzebehandlung unter Zerstörung der geordneten Strukturen eliminiert werden. Als Ergebnis dieser Behandlung werden die Charakteristika der Kristallisation und ihre quantitativen Parameter denen von nicht-orientierten Polypropylenen ähnlich.

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Résumé Les conditions de la fusion du polypropylène à orientation biaxiale (BOPP) ont un effet très important sur le déroulement de la cristallisation isotherme ou non, à partir du produit fondu. On montre que la cristallisation s'effectue suivant deux mécanismes. Suivant les conditions de fusion, les deux mécanismes peuvent intervenir seuls ou simultanément (cristallisation double). Le mécanisme à grande vitesse observé lors de la cristallisation isotherme, et lors de la cristallisation non isotherme avec une faible surfusion, peut être attribué à la structure ordonnée, préservée dans le produit fondu après la fusion, probablement sous un état mésomorphe. Le second mécanisme correspond à la cristallisation à partir d'un produit fondu isotrope.La cristallisation anormale des échantillons de BOPP peut être éliminée par un traitement thermique énergique, par destruction des structures ordonnées. Comme résultat de ce traitement, les paramètres quantitatifs et les caractéristiques de la cristallisation deviennent similaires à ceux du polypropylène non orienté.

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- , . , . , , ( ). , , , , , . . . , , .

     

Creation of acid sites by La-ions in L zeolite

The creation of strong acid sites in alkaline K-L-zeolites on ion-exchanging with La-ions is reported. Acidity measurements have been carried out by temperature programmed desorption of adsorbed ammonia. Reaction data which confirm the creation of acid sites are also reported.

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- K-L La. - . , .

     

On the mechanism of isocyanate preparation by the phosgenation reaction

A new mechanism of the transformation of amine hydrochlorides into isocyanates during the phosgenation process was proposed on the basis of radioisotope exchange between p,p'-diamino-1,2-diphenylethane dihydrochloride (³⁶Cl) and phosgene. The reaction proceeds through a transition complex of amine hydrochloride and phosgene, formed on the surface of the hydrochloride crystals.

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(³⁶Cl) ,'--1,2- . , .

     

IR and thermal studies on lithium oxomolybdenum(VI) oxalate

A new molybdenum(VI) complex, Li₂[Mo₂O₆(C₂O₄)] · 2 H₂O (LMO), was prepared and characterized by chemical analysis and IR spectral studies. Its thermal decomposition was studied by using TG and DTA techniques. LMO loses its two moles of water between 75 and 170° to give the anhydrous product, which decomposes in three stages between 240 and 380°. The first two stages occur in the temperature ranges 240–280° and 280–305°, to give intermediates with the tentative compositions Li₆[Mo₆O₁₉(C₂O₄)₂] and Li₆[Mo₆O₂₀(C₂O₄)], respectively. In the third stage, which extends up to 380°, Li₆[Mo₆O₂₀(C₂O₄)] decomposes to give the end-product, Li₂Mo₂O₇.

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Zusammenfassung Ein neuer Molybdän(VI)-Komplex der Formel Li₂[Mo₂O₆(C₂O₄)] · 2 H₂O (LMO) wurde dargestellt und durch chemische Analyse und IR-spektroskopisch charakterisiert. Die thermische Zersetzung dieses Komplexes wurde mittels TG und DTA untersucht. LMO verliert die zwei Wassermoleküle zwischen 75 und 170° unter Bildung des wasserfreien Produktes, das zwischen 240 und 380° in drei Stufen zersetzt wird. Die in den Temperaturbereich von 240–280° und 280–305° verlaufenden ersten zwei Reaktionsschritte ergeben Intermediäre der tentativen Zusammensetzung Li₆[Mo₆O₁₉(C₂O₄)₂] bzw. Li₆[Mo₆O₂₀(C₂O₄)]. In dem sich bis 380° erstreckenden dritten Reaktionsschritt wird Li₆[Mo₆O₂₀(C₂O₄)] unter Bildung des Endproduktes Li₂Mo₂O₇ zersetzt.

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Li₂[MO₂O₆(C₂O₄] · 2 ₂ . . - 70–170° , , 240–380°. 240–280° 280–305° - Li₆[Mo₆O₁₉(C₂O₄)₂] Li₆[Mo₆O₂₀(C₂O₄)]. - 380° Li₂Mo₂O₇.

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The authors are grateful to Prof. S. N. Tandon, Head of the Chemistry Department, for providing the research facilities.     

Inductive hydrogen formation in the oxidation of ascorbic acid by nitrosylpentacyanoferrate(II)

In the first period of the reaction at pH 8 slow evolution of CO₂ and N₂O was observed. After gas evolution ceased, on adding NaOH, formation of N₂O again and, unexpectedly, H₂ was found. The amount of H₂ was measured as a function of reaction conditions. Illumination with visible light and the excess of the oxidant promote hydrogen evolution. The experiments in D₂O resulted in H₂, HD and D₂. The non-statistical isotope distribution was interpreted by a kinetic isotope effect.

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pH=8 CO₂ N₂O. NaOH, N₂O , , H₂. H₂ . . D₂O H₂, HD D₂. .

     

Silicoaluminophosphate molecular sieves: Characterization of textural and acidic properties

The silicoaluminophosphate SAPO-37 as well as ZSM-20 zeolite have a faujaside-like structure and are potentially useful as catalysts. We report in this work different procedures to decompose the organic template occluded in SAPO-37. The texture of the final products was analyzed by means of nitrogen adsorption. The acid properties of SAPO-37 and ZSM-20 were also compared by IR measurements of adsorbed pyridine and related to the acidic properties of the presently commonly used cracking catalyst zeolite Y.

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-37, ZSM-20 . , -37. . -37 ZSM-20 - . , .

     

Reactivity of coordinated O2? ion-radicals in the oxidation of organic compounds

By the flow ESR method, the rates of the reaction of the radical complex Ti(IV)(O ₂ ^– ) with some aromatic compounds in aqueous solution have been measured. An elementary step of these reactions seems to be one-electron oxidation with the formation of a substrate cation-radical.

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- Ti(IV)(O ₂ ^– ) . - -.

     

Effect of molecular rotations on capture in the ion-linear dipole system

It has been established that cation distribution in kaolinite, which becomes close to that in Na–A zeolite due to mechano-chemical activation and thermal treatment, promotes zeolite crystallization. Optimal conditions for calcining the initial kaolinite to produce zeolites are established.

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, Na–A . .

     

Liquid-phase hydrogenation of cyclohexene by dihydrogen in the presence of dimolybdenum tetraacetate

Catalytic liquid-phase hydrogenation of cyclohexene in DMF by dihydrogen in the presence of dinuclear bridged complex Mo₂(OAc)₄ has been studied. A kinetic equation for the steady-state rate of cyclohexene hydrogenation and the activation parameters are suggested.

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Mo₂(OAc)₄. .

     

Correlations between photosorption and photocatalytic activities of alkali metal halides

An analysis of the correlation suggests that the common stages in photosorption, photooxidation and photodecomposition of some simple molecules on alkali metal halides are connected with catalyst photoexcitation.

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, , , .

     

Determination of liquid vapour adsorption and desorption on and from solids by means of the derivatograph II

Studies of water adsorption and desorption on silica gel with a modified derivatograph are described. The dynamic gas chromatography step profile method was used to determine isotherms of adsorption and desorption from the TG curve. The obtained isotherms agree with those from other methods. The properties of surface liquid layers can be investigated by this method.

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Zusammenfassung Die Untersuchung der Adsorption und Desorption von Wasser an Silikagel mittels eines modifizierten Derivatographen wird beschrieben. Die dynamische gaschromatographische Stufenprofilmethode wurde zur Bestimmung der Ad- und Desorptionsisothermen aus den TG-Kurven herangezogen. Die erhaltenen Isothermen stimmen gut mit denen nach anderen Methoden bestimmten überein. Die Eigenschaften flüssiger Oberflächenschichten können mit dieser Methode untersucht werden.

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. . , . .

     

Surface reorganization of carbon supported cobalt catalysts during CO chemisorption

Different monometallic catalysts containing Fe, Co or Ni and a Fe–Co bimetallic catalyst have been prepared by impregnation of an activated carbon. The formation of subcarbonyl species during CO adsorption, as detected by the slow adsorption rate, was observed. From the CO adsorption isotherms, the possibility of a surface reorganization in the Co catalysts induced by the interaction with CO is deduced.

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, Fe, Co Ni Fe–Co . CO . Co , CO.

     

51V-NMR spectra of vanadates and oxosulfato-vanadates of alkali metals

A relation between the type of vanadium environment and the chemical shift anisotropy in the⁵¹V-NMR spectra has been established. The results obtained are compared with spectra of real catalysts.

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⁵¹V , .

     

XPS study of ethylene adsorption on Ir (110)

The state of adsorption layers and adsorption kinetics of C₂H₄/Ir (110) at 300–1000 K has been studied using XPS method.

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C₂H₄/Ir (110) 300–1000 K.

     

Reactivity of radical complexes Zr(IV) (O2?) in electron transfer reactions

Rate constants of the reactions of the radical complex Zr(IV) (O ₂ ^– ) with Fe(II), Ti(III), resorcinol, guaiacol and ascorbic acid in aqueous solutions have been measured by the ESR flow method. They are similar to the values obtained for the radical complex Ti(IV) (O ₂ ^– ).

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Zr(IV)(O ₂ ^– ) , , , . , Ti(IV)(O ₂ ^– ).