Thermal stability of substituted poly-xylylenes

The insertion of meta units in the chain of poly-p-xylylene decreases both the onset temperature of oxidative degradation and the rate of decomposition.Functionalization of the polymer with chlorine and sulphonic groups makes the chain more resistant to high temperature treatments, notwithstanding the low stability of the substituent groups.

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Zusammenfassung Die Einführung von Metaeinheiten in die Kette von Poly-p-xylen setzt sowohl die Einsetztemperatur des oxydativen Abbaues als auch die Zersetzungsgeschwindigkeit herab. Die Einführung von Chlor und Sulfogruppen erhöht trotz der geringen Stabilität der Substituenten die Temperaturbeständigkeit der Kette.

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- -- . , .

     

Kinetics of reactions in solution: Method for the treatment of data from non-isothermal chemical kinetic experiments

A new method is proposed for the treatment of kinetic data derived from non-isothermal kinetic experiments for the determination of the parameters of the Arrhenius equation. The results obtained from its application show the excellent precision of this method.

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. , , .

     

Partial oxidation of methane over phosphate

Partial oxidation of methane over unpromoted and promoted iron phosphate catalysts was investigated in the temperature range of 873–953 K in a flow reactor. Using XRD and IR techniques, the bulk and surface structure of the given catalysts have been studied. The modification functions of lanthanum phosphate for partial oxidation of methane were also examined.

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873–953 . - -. .

     

Application des methodes thermoanalytiques a l'etude des solides divises

Résumé L'application des méthodes thermoanalytiques à l'étude des solides finement divisés s'avère dans certains cas plus efficace que celle de la diffraction des rayons X. A propos d'oxydes constitués de cristallites de quelques dizaines d'angströms, nous montrons comment la TG et l'ATD ont permis une caractérisation de phases. Celles-ci, qualifiées généralement et hâtivement «d'amorphes» n'avaient pu, pour la plupart, être mises en évidence jusque là.

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The application of thermoanalytical methods to study finely-divided solids is found more efficient in some cases than X-ray diffraction. For oxides whose crystallite size is in the range of a few ten angströms, it is shown how TG and DTA have allowed phase identifications. The majority of these phases, called generally and prematurely amorphous had not previously been yet reported.

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Zusammenfassung Der Einsatz thermoanalytischer Methoden zur Untersuchung fein verteilter Feststoffe erweist sich in gewissen Fällen als wirksamer als die Anwendung der Röntgendiffraktion. An Hand von Oxiden, welche aus Kristalliten der Grössenordnung einiger zehn Angström bestehen, wird gezeigt, in welcher Weise die Thermogravimetrie und die Differentialthermoanalyse eine Charakterisierung der Phasen gestatten. Die im allgemeinen voreilig als amorph bezeichneten Phasen konnten größtenteils bis jetzt nicht nachgewiesen werden.

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, - , , , . , ** , , . , , .

     

Li/MgO catalysts. III. Effect of precursor salts on the catalytic activity in methane oxidative coupling

Oxidative coupling of methane has been studied on Li/MgO catalysts prepared from three different MgO precursors and from lithium carbonate or nitrate. In samples prepared from Li₂CO₃, the persistence of this on the support surface favors formation of carbon oxides.

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Li/MgO, MgO . , Li₂CO₃, .

     

Alkylation of toluene with methanol over rare earth forms of Na?X, FAU and Na?Y, FAU

(La^ex, Na)-X, FAU, (Na, Y^ex)-X, FAU, (La^ex, Na)-Y, FAU and (Na, Y^ex)-Y, FAU have been shown to be active and selective catalysts for the alkylation of toluene with methanol. Na–X, FAU and Na–Y, FAU modified by La³⁺ have the highest activity but a very stable activity was reached only on Y³⁺ forms. (Na, RE^ex)-X FAU series prefer ortho-substitution while (Na, RE^ex)-Y, FAU para-substitution. Brönsted acid centers and their strength are responsible for substition.

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, (La^ex, Na)-X, FAU, (Na, Y^ex)-X, FAU, (La^ex, Na)-Y, FaU (Na, Y^ex)-Y, FAU . Na–X, FAU Na–Y, FAU, La³⁺, , , Y³⁺. (Na, RE^ex)-X, FAU -, (Na, RE^ex)-Y, FAU--. .

     

Collisional energy transfer in the two-channel decomposition of 1,1,2,2-tetrafluorocyclobutane and 1-methyl-2,2,3,3-tetrafluorocyclobutane, II. Gas/wall collisions

The efficiency of gas/wall vibrational energy transfer has been studied over the temperature range 800–1100 K by the variable encounter method. The average energies transferred per deactiviting collisions with the wall were determined at 800 K to be 3200 cm^–1 and 2900 cm^–1 for the 1,1,2,2-tetrafluorocyclobutane (TFCB) and 1-methyl-2,2,3,3-tetrafluorocyclobutane (MTFCB) molecules, respectively. This energy increased strongly with decreasing temperature. A comparison is made of with previous results for related molecules.     

Nature of extended defects of CuO

For the first time, using high-resolution electron microscopy, extended defects (twins, screw dislocations and microdistortions) of disperse CuO have been found. Their structure is described.

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CuO -, .

     

IR spectra of oxygen adsorbed on SnO2

IR spectra of oxygen adsorbed on SnO₂ with and without lattice defects have been studied. At low temperatures oxygen is adsorbed on defect SnO₂ in two forms of O ₂ ^– . This supports the earlier results obtained by ESR. The low-temperature forms of adsorbed oxygen (unrevealed in ESR spectra) were detected on defectless SnO₂. High-temperature forms of adsorbed oxygen appear in the IR-spectra as bands due to vibrations of the cation-oxygen bond.

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- SnO₂. , O ₂ ^– , . SnO₂ .

     

Oxidation of propylene to acrylic acid on a Fe?Mo?Bi oxide system

Data obtained in a flow reactor show that iron(III) molybdate doped by bismuth can oxidize propylene to acrylic acid directly in one step. Part of the catalyst works in a partially reduced form and in the preparation of the catalyst the surface acidity must be controlled.

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, , (III), , . .

     

Surface hydration of crystalline and amorphous silicas

The surface properties of three SiO₂ samples, one crystalline (quartz) and two amorphous, with a large difference in particle size, have been investigated by thermal analysis, adsorption calorimetry and infrared spectroscopy. The variation in the silanol group population upon thermal treatment has been followed via the evolution of the i.r. bands at 3745–3750 cm^–1 (free hydroxyl groups) and 3650-3550 cm^–1 (adjacent pairs of SiOH) and the evolution of the heat of adsorption of water with coverage on the outgassed samples.The adsorption capacities increase in the sequence high surface area amorphous sample T=673 K) brings about dehydroxylation leaving only isolated silanols on the high surface area amorphous silica, and partial dehydroxylation of the low surface area material. Quartz is totally hydrophilic, as its regular structure probably stabilizes the hydroxyl layers at the surface.

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Zusammenfassung Die Oberflächeneigenschaften von einer kristallinen (Quarz) und zwei amorphen SiO₂-Proben mit großen Unterschieden in der Partikelgröße wurden durch thermische Analyse, Adsorptionskalorimetrie und Infrarotspektroskopie untersucht. Bei thermischer Behandlung eintretende Veränderungen in der Silanolgruppenpopulation wurden durch Messung der IR-Banden bei 3745–3750 cm^–1 (freie Hydroxylgruppen) und 3650–3550 cm^–1 (benachbarte SiOH-Paare) und der Adsorptionswärme von Wasser an ausgeheitzten Proben untersucht. Die Adsorptionskapazitäten nehmen in folgender Reihenfolge ab: amorphe Probe mit großer Oberfläche > amorphe Probe mit geringer Oberfläche > Quarz. Dehydroxylierung der Oberfläche hat zunehmenden hydrophoben Charakter (Gestalt der Isothermen, Adsorptionswärme kleiner als Kondensationswärme von Wasser) zur Folge. Bei der gleichen thermischen Behandlung (673 K) werden bei amorphen Siliciumdioxid mit großer Oberfläche eine nur isolierte Hydroxylgruppen zurücklassende Dehydroxylierung und bei Material mit kleiner Oberfläche eine teilweise Dehydroxylierung beobachtet. Quarz ist vollkommen hydrophyl, da die reguläre Struktur wahrscheinlich die Hydroxylschichten an der Oberfläche stabilisiert.

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, , (), — . 3745–3750 ^–1 ( ) 3650–3550 ^–1 ( SiOH), . < < . ( , ). (T=673 K) . , , , .

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This research was supported by the Ministry of Public Education within a national programme relating to the structure and reactivity of surfaces.     

Interaction between metal and support: Effects of support acidity on adspecies of co over Ru

Supported Ru/X catalysts (X: SiO₂, Al₂O₃, SiO₂·Al₂O₃, HY) have been investigated by IR and TPR (temperature programmed reduction). Due to interaction between Ru and Lewis or Brönsted sites of the support, the Ru sites become electron-deficient. Stronger acidity of the support makes the Ru sites more electron-deficient, and as a result, adspecies of Ru⁺ (CO)₄ or Ru⁺(CO)₂ can occur more easily.

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Ru/X (X:SiO₂, Al₂O₃, SiO₂·Al₂O₃, HY) - . Ru . , Ru⁺(CO)₄ Ru⁺(CO)₂.

     

Excess heat of mixing of binary mixtures of pyridine withn-alkanes at 313.15 K

The molar excess enthalpies of binary mixtures of pyridine with C₆–C₉ n-alkanes have been measured at 313.15 K in the entire composition range. The measuredH ^E values were compared with those calculated by means of the Prigogine-Flory-Patterson theory and by the ERAS method.

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Zusammenfassung Die molaren Überschußenthalpien binärer Mischungen von Pyridin mit C₆–C₉ n-Alkanen wurden bei 313,15 K im ganzen Zusammensetzungsbereich gemessen. Die gemessenenH ^E Werte wurden mit denen verglichen, die mit Hilfe von Prigogine-Flory-Patterson Theorie und nach der ERAS-Methode berechnet wurden.

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313,5 n- (₆-₉) ce . -- (ERAS).

     

Effect of composition of the solvent on the selectivity of competitive hydrogenation of 2-methyl-3-butene-2-ol and 1-hexene

The selectivity of competitive hydrogenation of 2-methyl-3-butene-2-ol and 1-hexene on 5% Pt on silica gel catalyst at 20°C and atmospheric pressure was investigated, and the effect of changes in the composition of the solvent on the selectivity of hydrogenation was examined. Three solvent systems have been used: methanol-water, 1-heptanol-cyclohexane and ethanol-cyclohexane mixtures. The causes underlying changes in the selectivity of hydrogenation with changing composition of the solvent are discussed.

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2--3--2- 1- 5% Pt 20°C . . 1- . .

     

Thermodynamic properties of liquids,including solutions

Summary A new theoretical treatment of the dependence of surface pressure on the concentration of linear polymer molecules in a monolayer is presented. The development follows closely that in the author's new theory of the thermodynamic properties of three-dimensional solutions.

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Zusammenfassung Es wird eine neuartige theoretische Untersuchung vorgelegt über die Abhängigkeit des Oberflächendruckes von der Konzentration an linearen Makromolekülen in einer monomolekularen Schicht. Die Entwicklung schließt sich eng an des Autors neue Theorie der dynamischen Eigenschaften von dreidimensionalen Lösungen an.

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Glossary A Area of the monolayer surface - B ₁,B ₂ Functions in the expansion of in powers ofm/A. See [38] - E Intermolecular energy in the monolayer. See [2]. It is negative for attraction energy - G Gibbs energy. See [1] - H Enthalpy. See [1] - K Equilibrium constant, defined by [3]. Equal to 1 for perfect randomness of segment contacts - K A constant, related toK by [8] - M ₁,M ₂ Molar masses (molecular weights) of substrate and polymer - N _a Avogadros number=6.0225×10²³ mol^–1 - R Molar gas constant=8.3143 JK^–1 mol^–1 - S Entropy. See [1] - S _cc Correction to the combinatorial entropy to allow for imperfect randomness - S _or Contribution to the entropy of mixing to allow for concentration dependence of entropy of orientation, vibration and rotation of molecules and segments - S _rm Combinatorial entropy of mixing, assuming perfect randomness - T Temperature in kelvins - a ₀ ,a ₀ Areas in monolayer occupied by one mole (Avogadros number) of solvent and polymer segments, respectively. See [10] - g _K A function ofK and the concentration, defined by [7] - m Mass of polymer in the monolayer - m/A Mass/area ratio. Related to area fractions by [14] - n Average number of segments per polymer molecule - r _a =a ₀ /a ₀ Segment area ratio. See [16] - r = ₀ / ₀ Contacting segment outline ratio. See [16] - r _a/ =r _a /r See [16] - r _/a =r /r _a See [16] - x ₁,x ₂ Mole fractions of solvent and polymer in the monolayer - z ,z Contacting segment outline fractions, defined by [9] - Surface pressure required to keep monolayer in areaA - , Designating solvent and polymer segments, respectively - , , Energy per unit length of contact between pairs of segments of the type indicated. See [6] - Energy change when two unit lengths of contacts between like segments are replaced by two unit lengths of contacts between unlike segments. Defined by [6] - Energy parameter, defined by [5] - ₁, ₂ Densities of the pure components (mass/volume) - _m Surface density of polymer in a completely filled monolayer (mass/area) - , Sum of the contacting outlines, for segments of the type indicated, in the monolayer - ⁰ , ⁰ Average contacting outline per segment, of the type indicated - , , Sum of the contact lengths, for contacts of the type indicated, in the monolayer - ₁, ₂ Area fractions, measuring the fractions of the monolayer area occupied by solvent and polymer molecules, respectively.     

Comparison of different chemical modifiers for the direct determination of arsenic in sea water by electrothermal atomic absorption spectrometry

A comparative study of different chemical modifiers for the direct determination of arsenic in real and in synthetic sea water samples of high (72.8) and low (34.2) salinity was carried out. The use of lanthanum chloride and magnesium nitrate (LOD=3.0 gl^-1) offers good recoveries for low salinities, while for high salinities an enhancement higher than 200% was obtained, rendering this method unsuitable for sea water samples. The use of silver nitrate (LOD=2.0 gl^-1) produces unfavourable analytical recoveries, around 150 and 300% for synthetic sea water of low and high salinity. Zirconium oxychloride (LOD=1.8 gl^-1) and palladium nitrate alone or combined with magnesium nitrate and reducing agents (LOD=1.1–1.3 gl^-1) produce analytical recoveries close to 100% for all arsenic concentration tried over all salinities; thus, a single calibration curve using aqueous standard solutions may be applied to the analysis of sea water samples over all salinities. Finally, the addition of reducing agents and magnesium nitrate to palladium does not improve the sensitivity.     

Structure of a new chalcone ammothamnidin fromAmmothamnus lehmanni

A new chalcone ammothamnidin with the composition C₂₅H₂₈O₄, mp 112–114°C [] _D ²⁰ + 4.5° (methanol) has been isolated from the epigeal part and roots ofAmmothamnus lehmanni Bge. On the basis of chemical transformations and IR, UV,¹H and¹³C NMR, and mass spectra it has been shown that ammothamnidin has the structure of 2,2,4-trihydroxy-3-(2-isopropenyl-5-methylhex-4-enyl)chalcone.A. Navoi Samarkand State University. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 445–450, July–August, 1983.     

Catalytic oxidation of monosubstituted phenols by hydrogen peroxide

Studies of kinetic peculiarities in hydroxylation of phenols by H₂O₂ in the presence of ferric sulfate have revealed general regularities of this process. A scheme of this process is suggested accounting for the stepwise conversion of Fe³⁺ into various complex forms. The reaction is suggested to take place in the coordination sphere of Fe³⁺.

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H₂O₂ . . , Fe³⁺ .