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 -, .

     

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.     

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).

     

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--. .

     

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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- -- . , .

     

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 . - -. .

     

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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. , , .

     

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.     

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 .

     

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.

     

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), , . .

     

The determination of boron in biological materials by neutron irradiation and prompt gamma-ray spectrometry

A prompt-gamma neutron activation technique has been developed using the (n, ) apparatus situated at the O degree through-tube of the Imperial College CONSORT II Reactor with a thermal neutron flux at the target position of approximately 2×10⁶ n cm^–2 sec^–1, and a Compton-suppression system involving a lithium-drifted germanium (Ge(Li)) detector and a sodium iodide anti-Compton shield. Boron levels of 1–5 g g^–1 (detection limit 0.05 g B for 10,000 sec period of measurement) can be attained using the Compton-suppression system with graphical inter-polation correction for the 472 keV sodium-ray peak contribution to the Doppler-broadened 478 keV boron gamma-ray peak resulting from the¹⁰B(n, )⁷Li reaction. Very good agreement is reached for boron levels compared using this system for various Standard Reference Materials and other published values. Measurement of the boron content of bone and tooth samples from rheumatoid arthritis individuals shows lower levels, (p<0.05); 16.13±7.53 g g^–1, when compared with a control population; 19.79±4.18 g g^–1. A positive correlation existed between the boron content of bone and tooth material for each study group. Results indicate that boron availability may be associated with rheumatoid arthritis.     

Studies of the reactions of Br(2P3/2) and Br(2P1/2) with SiH4

Photobromination of SiH₄ under uv-irradiation at various wavelengths has been studied. Rate constants for the elementary reactions Br(²P_3/2)+SiH₄HBr+SiH₃ (k=3.2×10^–11 exp(–21.8±2.5)/RT, cm³/s) and Br^* (²P_1/2)+SiH₄HBr+SiH₃ (k^*=(3±1)×10^–13 cm³/s) have been determined in the temperature range from 300 to 415 K.

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- . Br(²P_3/2)+SiH₄HBr+SiH₃, k=3,2×10^–11 exp (–21,8±2,5)/RT ³/ Br^*(²P_1/2)+SiH₄HBr+SiH₃, k^*=(3±1)×10^{–13 3}/ 300–415 K.

     

Kinetics of Free Radical Generation in the Catalytic Oxidation of Methanol

The formation of free radicals over the surface of platinum-containing catalysts in the methanol oxidation reaction depending on the temperature, the composition of the reaction mixture, and the procedure used for introducing platinum was studied by the matrix isolation method technique. The nature and transformations of surface intermediates depending on the temperature and the presence of oxygen in the gas phase were studied by Fourier transform IR spectroscopy. The main surface intermediate was the methoxy group. The following three types of these groups were stabilized in alumina-based catalysts: (I) CH₃O–Al_oct (_s(–) = 2806 cm^–1), (II) CH₃O–Al_tetr (_s(–) = 2825 cm^–1), and (III) CH₃O < (Al)₂ (_S(–) = 2845 cm^–1, _s(–) = 1460 cm^–1, _s(–) = 1440 cm^–1, r _|| (₃) = 1185 cm^–1, and (–) = 1095 cm^–1). At the same time, isolated methoxy groups (_as(–) = 2997 cm^–1, _as(–) = 2959 cm^–1, _s(–) = 2857 cm^–1, and (₃) = 1450 cm^–1) and hydrogen-bonded groups ((–) = 3400–3550 cm^–1), which resulted from chemisorption at siloxane bridges, were stabilized in silica gel–based catalysts. It was found that CH₃O and CH₃OO radicals were formed only over the surfaces of pure supports (SiO₂ and Al₂O₃) and their mechanical mixtures with platinum. The total concentration of radicals was described by an extremal function of the composition of reactants, whereas the relative concentration depends on the nature of the support. This is conceivably due to the effect of coordinatively unsaturated cations of the support, which are formed by dehydroxylation in the course of catalyst pretreatment. An increase in the rate of formation of gas-phase radicals on mixed catalysts was explained by special properties of the platinum/support interface region, at which surface intermediates were formed in superequilibrium concentrations under reaction conditions.     

Magnetic anisotropy of cyclopropane and epoxide rings

MO LCAO results are presented for the interatomic contribution to the anisotropy of the diamagnetic susceptibility; values of _d=–23.5 · 10^–6 and _d=–13.8 · 10^–6 cm³/mole are obtained for the cyclopropane and epoxide ring systems, respectively. The results are used to interpret PMR spectra in terms of the configuration and conformation of the and forms of caran-4-ol and two stereoisomers of caranone.     

Influence of substituents on hydrogenation of nitro groups in aromatic hydrocarbons catalyzed by rhenium thiocomplexes

Homogeneous hydrogenation studies of (NO₂)_1–2–C₆H_3–4–L nitro compounds (where L=–H,–NH₂,–COOH,–CHO,–OH,–CH₃ and –CH=CH–COOH) catalyzed by Re₂S₆TThio₃Cl₂ in dimethylformamide solutions at and T=343 K, have revealed that the reaction is enhanced by electron-acceptor substitutents and hindered by electron-donor ones.

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(NO₂)_1–2–C₆H_3–4–L, L=–H,–NH₂,–COOH,–CHO,–OH,–CH₃,–CH=CH–COOH, Re₂S₆Thio₃Cl₂ 343 . , .

     

Magnetic properties of transition metal ion cubic 5T2 terms in axial ligand fields

The theory of magnetic anisotropy and susceptibility is worked out for cubic ⁵T₂ terms, the degeneracy of which is partially lifted by a ligand field component of axial symmetry as well as by spin-orbit coupling. Matrix elements are calculated by application of the method of Abragam and Pryce to a set of M.O. based wave-functions. The anisotropy in covalency of the metal-ligand bond and in spin-orbit coupling is taken into account. Numerical values of principal magnetic moments, P and P , are calculated as function of kT/, /, and .The theoretical results are employed in a rigorius analysis of existing single crystal magnetic data on high-spin iron(II) compounds. For (NH₄)₂Fe(SO₄)₂·6 H₂O, =–100 cm^–1, =1070 cm^–1 and =0.8 to 0.6 is obtained. For FeSiF₆·6 H₂O, =–80 cm^–1, =–760cm^–1 at 77.3K and –580 cm^–1 between 20.4 and 1.57K, and 0.7 is derived. No unique fit is possible for K₂Fe(SO₄)₂·6 H₂O. The data are reproduced to better than ±1% in most cases. The limitations of the approach are stressed.

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Zusammenfassung Die Theorie der magnetischen Anisotropie und der magnetischen SuszeptibilitÄt eines ⁵ T ₂ Grundterms im oktaedrischen Ligandenfeld wird für den Fall entwickelt, da\ die Entartung unter dem Einflu\ einer axial-symmetrischen Feldkomponente sowie der Spin-Bahn-Wechselwirkung teilweise aufgehoben ist. Eigenfunktionen werden auf der Grundlage der M.O.-Theorie aufgestellt, Matrixelemente mittels der Theorie von Abragam und Pryce ermittelt. Der Anisotropie der Metall-Ligand-Bindung sowie der Spin-Bahn-Kopplung wird Rechnung getragen. Numerische Werte für die magnetischen Hauptmomente P und P werden in AbhÄngigkeit von kT/, / und berechnet.Die Ergebnisse der Theorie werden für eine genaue Analyse der verfügbaren magnetischen Daten aus Messungen an Einkristallen magnetisch normaler Eisen(II)-Verbindungen verwendet. Für (NH₄)₂Fe(SO₄)₂·6 H₂O werden =–100 cm^–1, = 1070 cm^–1 und = 0,8 bis 0,6 erhalten. Für FeSiF₆·6 H₂O ergeben sich =–80 cm^–1, =–760 cm^–1 bei 77,3K und =–580 cm^–1 zwischen 20,4 und 1,57K sowie 0,7. Die experimentellen Daten können in den meisten FÄllen auf ±1% genau oder besser wiedergegeben werden. Bei K₂Fe(SO₄)₂·6 H₂O gelang keine eindeutige Bestimmung der theoretischen Parameter. Die Grenzen der vorliegenden Behandlung werden kritisch diskutiert.

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Résumé La théorie de l'anisotropie magnétique et de la susceptibilité magnétique est développée pour les termes cubiques ⁵ T ₂, dont la dégénérescence est partiellement levée par une composante à symétrie axiale du champ de ligandes ainsi que par le couplage spin-orbite. Les éléments de matrice sont calculés à l'aide de la méthode d'Abragam et Pryce employée sur un système M.O. des fonctions d'onde de base. On a pris en consideration l'anisotropie de la liaison entre le metal et le ligand et aussi du couplage spin-orbite. Les valeurs numériques des moments magnétiques principaux P et P sont calculées en fonction de kT/, /, et .Les résultats théoriques sont employés dans une analyse détaillée des données magnétiques disponibles sur monocristaux des composés ferreux spin-élevés. Pour (NH₄)₂Fe(SO₄)₂·6 H₂O on a obtenu =–100 cm^–1, =1070 cm^–1 et =0.8 à 0,6. Pour FeSiF₆·6 H₂O on a eu comme résultat =–80 cm^–1, =–760 cm^–1 à 77,3 K et =–580 cm^–1 entre 20,4 et 1,57K avec 0,7. Les valeurs expérimentales sont réprésentées dans la plupart de cas plus précises que ±1%. Au cas de K₂Fe(SO₄)₂·6 H₂O une détermination unique était impossible. Les limites de cette approximation sont discutées.

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Postdoctoral Fellow, Theoretical Chemistry, 1963–1964.