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1.
Some images obtained by illuminating the Briggs-Raucher oscillating chemical reaction are illustrated. This reaction gives more distinct and contrasty images than the Belousov-Zhabotinskii reaction.
-. , , -.
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2.
Specificity of the bands at 1630–1620 cm–1 in IR spectra of coordinatively bonded pyridine has been studied. Three strong Lewis-type acid centers have been revealed on Al2O3 surface.
- 1630–1620 –1.
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3.
Two Pd-imidazole complexes have been synthesized following the reaction of PdCl2 and imidazole at 12 and 14 metal ligand ratios. Elemental and thermogravimetric analytical data obtained from these compounds illustrate that they have the formulae Pd(IMDAH)2Cl2 · 4H2O and Pd(IMDAH)3Cl2 (IMDAH = imidazole), respectively. The mechanism of thermal decomposition for these complexes in air involves initial dissociation of H2O and IMDAH ligands in the 120–340 °C range, subsequent dissociation of the chloride atoms to form PdO in the 530–570 °C range, and finally formation of Pd metal at 820–840 °C.
Zusammenfassung In einer Reaktion von PdCl2 mit Imidazol wurde bei einem metall-Ligandenverhältnis von 12 bzw. 14 zwei Pd-Imidazolkomplexe dargestellt. Auf Grund der Ergebnisse von Elementaranalyse und Thermogravimetrieuntersuchungen besitzen die Verbindungen die Formeln Pd(IMDAH)2Cl2·4H2O bzw. Pd(IMDAH)3Cl2 (IMDAH=Imidazol). Der Mechanismus der thermischen Zersetzung dieser Komplexe in Luft umschliesst eine anfängliche Dissoziation (Abgabe von Wasser und IMDAH-Liganden) im Temperaturbereich 120–340 °C, gefolgt von der Bildung von PdO unter Abspaltung der Chloratome bei 530–570 °C sowie die letztendliche Bildung von metallischem Pd bei 820–840 °C.

, 12 14, . , d()2l2· 42 d()3l2. 120–340°, 530–570°. 820–840°.
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4.
The hypothetical salts Li4SiN2O and Li7SiN3O were sought in the course of studies on the reactions of Li2SiN2 and Li5SiN3 with lithium oxide, and of LiSiNO with lithium nitride.
Zusammenfassung In einer Reihe von Studien der Reaktionen von Li2SiN2 und Li5SiN3 mit Lithiumoxid bzw. LiSiNO mit Lithiumnitrid wurde nach den hypothetischen Salzen Li4SiN2O und Li7SiN3O gesucht.

Li2SiN2 Li5SiN3 LiSiNO Li4SiN2O Li7SiN3O.
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5.
Studies of the liquid-phase oxidation of dibenzyl ether in the presence of 12 acetylacetonates of 3d metals and a comparative analysis of the dependence of the catalytic activity and selectivity of chelates on the atomic number and valence state have been carried out.
12 3d . .
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6.
In the region of intrinsic rutile adsorption, CO oxidation follows a redox mechanism via the interaction of CO with O ion-radicals, and the photocatalytic activity is determined by the density of 2p states close to the top of the valence band.
CO CO - O, 2- .
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7.
The oxidation of ethanol on CuO, CuO/Al2O3 and Pt/Al2O3 catalysts has been studied at various concentrations of alcohol, oxygen and water vapor in the reaction mixture. The reaction order and activation energies have been determined for both complete and partial oxidation processes. A consecutive oxidation scheme is suggested.
CuO, CuO/Al2O3 Pt/Al2O3 , . . .
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8.
    
The kinetics of the reductive decomposition of the isoprenepalladium -allyl complex [ClPdC5H8OCH3]2 by methylate ions in methanol, producing unsaturated methyl esters, has been studied calorimetrically. The autocatalytic character of the process has been established and the kinetic equation determined. The influence of methylate and chloride ion concentrations on the reaction rate has been examined.
- [ClPdC5H8OCH3]2, - , . . . - - .
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9.
The effect of the vanadium compounds [VO(phthalocyanine)], [VO(salen)] [salen=N,N-ethylenebis(salicylideneiminate)], petroporphyrins, and metal-free phthalocyanine on the hydrodesulfurization of thiophene over a Co/Mo/Al2O3 catalyst (350°C, 1 atm) is described. The compound [VO(salen)], which decomposes, acts as a promoter at low V (0.1–0.2 wt. %); the other compounds deactivate the catalyst, an effect which is due to the whole molecule binding to the catalyst in the same way as a nitrogen base.
[VO()], [VO()] [=N,N-- ()], , , Co–Mo/Al2O3 (350°C, 1). [VO()], , V (0,1–0,2 . %-); , , .
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10.
A chemiluminescent method was used to measure generation rates of active intermediates in the interaction of hemin with hydrogen peroxide with and without pyridine at pH=8–9. The effect of various inhibitors in these two cases has been examined.
pH=8+9. .
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11.
    
, 1.2·1018/2 3.6·1018/2, . , .
The endothermic stage of desctruction of Al2O3 crystal lattice begins with the adsorption of a monolayer of chloride and hydrogen ions (1.2×1018 m–2 and 3.6×1018 m–2, respectively). The abrupt change in the Al content of the solution is attributed to the release of low-coordinate aluminium ions from the environment of the cationic vacancies of the oxide lattice.
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12.
    
It has been found that there is a strong dependence of the rate of benzil hydrogenation on the structure and basicity of maines. This observation is interpreted in terms of heterolytic activation of hydrogen by cobaloxime.
. .
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13.
    
The heterogeneous oxidation of n-decane initiated by azo-bis(isobutyronitrile) on quartz surface has been investigated in the temperature range of 80–100°C. At 100°C after the complete consumption of the initiator the oxidation proceeds at a measurable rate. Though heterogeneous oxidation is in many aspects similar to liquid phase oxidation, differences can be observed due to the specific role of the surface.
80–100°C - , - (). 100°C . , , , .
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14.
It has been found that when the reaction is carried out at pressures of the reaction mixture ranging from 1 to 400 Pa, small surface coverages by adsorbed oxygen, carbonate groups and irreversibly adsorbed carbon-containing particles are obtained. Rate relaxations are due to the concentration variations of adsorbed oxygen and CO3ads groups.
, 1–400 , , . CO3.
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15.
NMR studies of the interaction between bis-acetylacetonato Co(II) and organotin compound SnPh2Cl2 (Ph=C6H5 ) in chloroform solutions with pyridine additive have revealed ligand exchange between the initial components to form Co(II) and Sn(IV) complexes with different numbers of ligands.
Co(II) SnPh2Cl2 (Ph=C6H5 ). , Co(II) Sn(IV) .
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16.
The oxidation of amino acids by chloramine-T (CAT) in HCl medium at 30°C indicates simultaneous catalysis by H+ and Cl ions in the HCl concentration range of 0.04–0.12 M. The reaction is first order with respect to concentrations [CAT], [H+] and [arginine], but zero order with respect to [histidine]. The rate depends also on Cl concentration following 0.7th order. At HCl concentrations >0.12 M, the rate equation is:w=k[CAT] [amino acid]0.6 and is independent of the [Cl]. A suitable mechanism has been suggested.
-T (CAT) HCl (30°C) H+, Cl [HCl]=0,04–0,12M. [CAT], [H+] [] []. [Cl]0,7. [HCl]>0,12M =k · [CAT][]0,6 [Cl]. .
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17.
During the grinding of quartz, water is adsorbed from the atmosphere, but this water gave no detectable thermal effect on DTA because it was evolved uniformly up to 1000°. However, in conjunction with an iron contaminant, the adsorbed water was involved in an oxidation reaction causing noticeable thermal effects for quartz powdered in a vibration mill constructed of steel parts. When powdered so finely that the - inversion peak at 573° had disappeared, annealing caused a partial redevelopment of the peak but recrystallization of disrupted quartz was too small an effect to give any detectable exothermic peak on DTA.
Zusammenfassung Während des Vermahlens von Quartz wird Wasser aus der Atmosphäre adsorbiert, jedoch ergab dieses Wasser keinen nachweisbaren thermischen Effekt in der DTA, da es bis zu 1000° gleichmässig freigesetzt wird. Im Zusammenhang mit einer Eisen-Verunreinigung wurde jedoch das adsorbierte Wasser in eine Oxidationsreaktion einbezogen, welche beim in einer aus Stahlteilen gefertigten Vibrationsmühle zerpulvertem Quartz nachweisbare thermische Effekte verursachten. Wenn so fein pulverisiert wurde, daß der --Inversions-Peak bei 573° verschwunden war, verursachte eine Wärmebehandlung eine teilweise Wiederentwicklung des Peaks, jedoch war die Rekristallisation des zerstörten Quartzes zu geringfügig um einen nachweisbaren exothermen Peak in der DTA-Kurve zu ergeben.

Résumé Lors du broyage du quartz, il se produit une adsorption de l'eau atmosphérique mais cette eau ne donne pas d'effet thermique décelable par ATD car elle se dégage régulièrement jusqu'à 1000°. Cependant, en présence de fer comme contaminant, l'eau adsorbée intervient dans une réaction d'oxydation qui donne des effets thermiques perceptibles dans le cas de quartz pulvérisé dans un vibrobroyeur en acier. Si le quartz est en poudre assez fine pour que le pic d'inversion - à 573° disparaisse, le recuit provoque la réapparition partielle du pic. La recristallisation du quartz est cependant trop faible pour donner un effet exothermique décelable par ATD.

, , 1000°. , , . - 573° , , , - .


We are grateful to the Science Research Council for supporting this work.  相似文献   

18.
The introduction of platinum in a protonic offretite causes a decrease of its activity for m-xylene isomerization and an increase of its constraint index. This is due to the blockage of the offretite channels by small platinum crystallites (<8 Å), as confirmed by the study of m-xylene adsorption.
- . (<8 Å), -.
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19.
ESR and IR-spectrosocpic studies of the effect of the state of vanadium ions on the IR-spectra of adsorbed CO have revealed complex formation of CO with V4+ (vCO at 2192 and 2205 cm–1) and V3+ (vCO at 2178 and 2185 cm–1) ions.
-- - CO. CO V4+ (vCO 2192, 2205 cm–1) V3+ (vCO 2178, 2185 cm–1).
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20.
The use of hydrogen-oxygen titration method to characterize platinum-nickel supported catalysts has shown that the number of oxidized or reduced nickel layers is dependent on the atomic composition. This phenome non involves dynamic changes of the surface probably by a spillover mechanism. A surface reaction scheme based on a previous work is proposed to explain the experimental results.
- - , . , , . , .
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