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1.
The dissociative and molecular forms of O3 adsorbed on nickel were studied by the density functional method (Becke3LYP exchange correlation functional). The energy profile of the ozone decomposition reaction (O3)gas (O3)ads (O2)ads+1/2O2 on the Ni10 surface cluster was calculated. As opposed to the weakly bound molecular form of oxygen on transition metals, ozone forms a tightly bound surface compound on the surface of nickel. It is attempted to evaluate the heat of oxygen adsorption on the defective surface of Ni using the model of the surface cluster Ni13 with a vacancy . The positions of the surface nickel atoms before and after their interaction with the adsorbate were calculated. It is shown that substantial relaxation of the surface nickel atoms takes place in the course of adsorption. The possibility of stabilization of the molecular ozone-like form of oxygen on the surface of transition metals in conditions of high oxygen coating extent is discussed.  相似文献   

2.
A cluster structure of the surface of a polypyromellitimide film was studied by the electron microscopy and ATR IR spectroscopy methods at different steps of consecutive treatment with aqueous solutions of an alkali and acid. The effective size and fractal dimension D of polyamidoacid clusters, as well as the degree s of the filling of the surface with the latter were calculated from the data of the electron microscopy as a function of the degree of imide group conversion into amidoacid units on the film surface. The s and D parameters were shown to increase with a rise in : s = 0.1–0.3 and D = 1.3–1.4 at < cr and s 0.6 and D 1.7 at > cr, where cr is a critical degree of conversion, which corresponds to the formation of a continuous physical network of polyamidoacid macromolecules or a percolation cluster. In a region close to cr (at < cr), the correlation length land the concentration C of the clusters vary according to the laws of the percolation theory for two-dimensional lattices: l (cr – ) and C (cr – ), where = 1.3 ± 0.1 and = 0.67 ± 0.05.  相似文献   

3.
The principles and the generalized equation of chemical algebra is extended to a Minkowskian substrateE endowed with its improper non-definite-positive metric, where the non-compact 6-parameter groupG of the Lorentz transformations operates. Given a map u,u(g) = (gu)m(g) onG, a line elementds 2 is formulated at each point marked by a vectoru. Assuming = 1 and m(g) : 0 g is a pure Lorentz transformation (without a spatial rotation), the isotropic hypothesis (m depends on a single parameter out of three inG) is first studied. In general,ds 2 does not define a Riemannian manifold unless one additional condition onm is imposed. Several relationships are established which are useful for the calculation of the metric tensor and the curvature tensor.  相似文献   

4.
The frequency shift, , of the O—H stretching mode in the IR spectra of the H-complexes of phenol with electron donor molecules BXi (B is the n- or -donor center and Xi are substituents; a total of eight series), the change in the Gibbs free energy, G, due to H-complexation, and the parameter (a measure of the ability of BXi molecules to donate an electron pair; two series) are determined by both the electrostatic interaction and charge transfer in the formation of H-complex. The , G, and values depend not only on the inductive and resonance effects, but also the polarizability of substituents characterized by the parameters.  相似文献   

5.
In aqueous solution, PM12–nVnO40 –(3+n) (M=Mo,W) hetero-polyanions provide a much faster oxidation of NO than mononuclear VO 2 + ions, yielding HNO2, NO 3 and reduced HPA.
, PM12–nVnO40 –(3+n) (M=Mo,W) , VO 2 + , NO HNO2 NO 3 .
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6.
BaSeO3·2·5H2O(I), PbSeO3· 2H2O(II) and CdSeO3·3.5H2O(III) were prepared and analysed. Their hygroscopicity and solubility was investigated. These compounds have high thermal Stability, as shown by their TG and DTA data. IR spectra show multi-dentate coordination of selenite to cations, due to considerable splitting of the asymmetric v3 and v4 bands of SeO 3 2 in the 780-730 cm–1 and 420-325 cm–1 region.Tentative structures have been proposed involving bridging oxygen atoms.
Zusammenfassung BaSeO3-2.5H2O(I), PbSeO3 · 2H2O(II) und CdSeO3· 3.5H2O(III) wurden hergestellt, analysiert sowie deren Hygroskopizität und Löslichkeit untersucht. TG- und DTA-Untersuchungen erweisen die hohe thermische Stabilität dieser Verbindungen. Die IR-Spektren zeigen mehrzählige Koordination von Selenit zu Kationen, was aus einer beträchtlichen Aufspaltung der antisymmetrischenv 3 undv 4 Banden von SeO 3 2 im Bereich 780-730cm–1 bzw. 420-325 cm–1 hervorgeht. Es wurden versuchsweise Strukturen mit überbrückenden Sauerstoffatomen vorgeschlagen.

BaSeO3· 2,5H2O, PbSeO3 · 2H2O CdSeO3 · 3,5H2O . . - , v 3 v 4 SeO 3 2 }- 780-730 420-325 –1. , .
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7.
The thermal decompositions of alkaline earth tris(oxalato)ferrates(III) (Mg, Ca, Sr and Ba) have been studied by Mössbauer spectroscopy and other techniques. During the thermal decomposition, dehydration occurs first, followed by reduction to iron(II) species, and oxides and ferrites (MFeIIIO4) are then formed at higher temperature. In the case of strontium tris(oxalato)ferrate(III), strontium ferrite (SrFeIVO4) is formed at 700°.
Zusammenfassung Die thermische Zersetzung von Tris(oxalato)ferraten(III) der Erdalkalimetalle (Mg, Ca, Sr, Ba) wurde durch Mössbauer-Spektroskopie und andere Techniken untersucht. Im Verlaufe der thermischen Zersetzung verläuft zunächst die Dehydratisierung, gefolgt von der Reduktion zu Eisen(II)-Species. Oxide und Ferrite (MFeIIIO4) werden danach bei höheren Temperaturen gebildet. Strontium-tris(oxalato)-ferrat(III) geht bei 700 °C in Strontiumferrit (SrFeIVO4) über.

() () , , ë . , , MFeIIIO4. 700° SrFeIVO4.
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8.
Résumé AlH3 a été synthétisé. La décomposition thermique de cet hydrure ainsi que la désolvatation de Al(AlH4)3, (C2H5)2O ont été étudiés par analyse thermogravimétrique. L'analyse thermique différentielle effectuée sur AlH3 montre un effet exothermique dû au passage à la forme AlH3 puis endothermique correspondant à la décomposition de la phase formée. Une structure type alanate est proposée pour AlH3 .
Aluminium hydride has been synthetised. Thermogravimetry has been used to investigate the thermal decomposition of this phase and the desolvation of A1(AlH4)3· (C2H5)2O. Differential thermal analysis of-AlH3 shows an exothermic effect due to transformation to -A1H3, followed by the endotherm of -AlH3 decomposition. A structure of alanate type is proposed for -AlH3.

Zusammenfassung -AlH3 wurde synthetisiert. Die thermische Zersetzung dieses Hydrids sowie die Desolvatation von Al(AlH4)3·(C2H5)2O wurden mittels Thermogravimetrie untersucht. Die Differentialthermoanalyse von-AlH3 zeigt einen dem Übergang in die AlH3 -Form entsprechenden exothermen und mit nachfolgenden endothermen Effekt, welcher der Zersetzung der gebildeten Phase entspricht. Eine Struktur von solvatfreien Alanat-Typ wird für-AlH3 vorgeschlagen.

- . l(l4)3. (C2H5)2O . l3 , l3. lH3 .


Ce travail a été effectué dans le cadre d'un contrat de recherches passé par le Laboratoire de Chimie Minérale avec la Direction des Recherches et Moyen d'Essai. Nous remercions bien vivement cet organisme ainsi que le Centre de Recherches ELF ERAP de Solaize de l'aide qu'ils nous ont apportée.  相似文献   

9.
Differential thermal and phase X-ray analyses have shown that MoO3 and Fe2V4O13 form a solid substitution solution, in which Mo6+ ions are incorporate into the crystal lattice of Fe2V4O13 in place of V5+ ions. The solubility limit of MoO3 in Fe2V4O13 at ambient temperature is 18 mole % of MoO3. The phase equilibria in the system Fe2V4O13-FeVMoO7, were also studied. Results are presented in the form of a phase diagram.
Zusammenfassung Durch DTA und Röntgenphasenanalyse wurde gezeigt, daß MoO3 und Fe2V4O13 Substitutionsmischkristalle bilden, in denen Mo6+-Ionen anstelle von V5+-Ionen in das Kristallgitter von Fe2V4O13 eingebaut sind. Die Löslichkeitsgrenze von MoO3 in Fe2V4O13 beträgt bei Umgebungstemperatur 18 Mol-% MoO3. Ebenfalls wurden die Phasengleichgewichte im System Fe2V4O13-FeVMoO7 untersucht. Die Ergebnisse sind in Form eines Phasendiagramms dargestellt.

- , 3 Fe2V4O13 , o6+ V5– Fe2V4O13. 3 Fe2V4O13 18 %. Fe2V4O13-FeVMoO7 .
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10.
The effect of reaction conditions on the methylmercaptan formation from dimethylsulfide in H2S catalyzed by -Al2O3 has been studied. The reaction is first order with respect to dimethylsulfide. It has been revealed that the maximum activity in this reaction is observed for the catalysts whose surface contains a large number of aprotonic acid centers and moderate-strength basic sites.
-Al2O3. , . . , , .
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11.
Interaction of quantum system S a described by the generalised × eigenvalue equation A| s =E s S a | s (s=1,...,) with quantum system S b described by the generalised n×n eigenvalue equation B| i = i S b | i (i=1,...,n) is considered. With the system S a is associated -dimensional space X a and with the system S b is associated an n-dimensional space X n b that is orthogonal to X a . Combined system S is described by the generalised (+n)×(+n) eigenvalue equation [A+B+V]| k = k [S a +S b +P]| k (k=1,...,n+) where operators V and P represent interaction between those two systems. All operators are Hermitian, while operators S a ,S b and S=S a +S b +P are, in addition, positive definite. It is shown that each eigenvalue k i of the combined system is the eigenvalue of the × eigenvalue equation . Operator in this equation is expressed in terms of the eigenvalues i of the system S b and in terms of matrix elements s |V| i and s |P| i where vectors | s form a base in X a . Eigenstate | k a of this equation is the projection of the eigenstate | k of the combined system on the space X a . Projection | k b of | k on the space X n b is given by | k b =( k S b B)–1(V k P})| k a where ( k S b B)–1 is inverse of ( k S b B) in X n b . Hence, if the solution to the system S b is known, one can obtain all eigenvalues k i } and all the corresponding eigenstates | k of the combined system as a solution of the above × eigenvalue equation that refers to the system S a alone. Slightly more complicated expressions are obtained for the eigenvalues k i } and the corresponding eigenstates, provided such eigenvalues and eigenstates exist.  相似文献   

12.
CH2O conversion over sodium-manganese oxide and oxychloride catalysts in methane dehydrodimerization have been studied under unsteady-state conditions at high temperatures (600–750 °C). It has been established that formaldehyde conversions produce deep oxidation (CO, CO2), condensation (C2H4, C2H6) and methanation products through CH3O formation and decomposition.
(600–750°C) CH2O - . , (CO, CO2) (C2H4, C2H6), , CH3O.
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13.
Developing the previously tested approach to the configurational and conformational analysis of cyclic chiral compounds based on a complex use of NMR spectra and molecular simulation, we determined the configuration 1R, 2R, 4R, 1S and conformational state of 2[1hydroxy1(4carbomethoxyphenyl) methyl]pmenthane3one, a minor product of the directed aldol reaction of (–)menthone with 4carbomethoxybenzaldehyde. The configurations of the cyclic chiral centers were determined by analysis of the spin–spin coupling constants of the protons of the cyclohexanone ring for the most probable conformations of alternative stereoisomers. The S configuration of the C (1) exocyclic chiral center was established from the different orientation of the benzene ring relative to the cyclohexanone fragment in alternative stereoisomers, as shown by semiempirical quantumchemical simulations (AM1 and PM3 methods), and from the observed difference in proton chemical shift between the examined hydroxyketone and the model (+)isomenthone (1R, 4Rdiastereomer).  相似文献   

14.
The effect of the carrier-gas (H2, N2, CO2 and air) and the influence of additives (H2S and water vapors) in the activation of Ni- and Cr-containing zeolites on their catalytic activity have been studied in toluene disproportionation.
- (H2, N2, CO2 ) (H2S ) , Ni Cr, .
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15.
The by-product phosphogypsum contains CaHPO4, H3PO4, Ca5(PO4)3F, Al2O3, Fe2O3, SiO2 etc. besides the main product CaSO4. By means of TG-DTA the thermochemical decomposition of pure phosphogypsum and phosphogypsum containing CaO, Al2O3, Fe2O3 and SiO2 in a reductive atmosphere was studied. The solid phase was examined by high-temperature thermomicroscopy, scanning electronmicroscopy, X-ray diffraction and other methods. It could be confirmed, that most of the admixtures undergo secondary reactions with CaO and CaS, modifying the decomposition rate of CaSO4.
Zusammenfassung Das Abfallprodukt Phosphatgips enthält neben dem Hauptbestandteil CaSO4 noch CaHPO4, H3PO4, Ca5(PO4)3F, Al2O3, Fe2O3, SiO2 und anderes. Die thermochemische Zersetzung von Phosphatgips bzw. Phosphatgips mit Zusätzen von CaO, Al2O3, Fe2O3 und SiO2 wurde in reduzierender Atmosphäre mittels TG-DTA untersucht. Die feste Phase wurde durch Hochtemperatur-Thermomikroskopie, Rasterelektronenmikroskopie, Röntgenbeugung und andere Methoden untersucht. Dabei wurde bestätigt, dass die meisten Beimengungen mit dem Calciumoxid bzw. -sulfid Sekundärreaktionen eingehen, wodurch auch die Zersetzungsgeschwindigkeit des CaSO4 beeinflusst wird.

, , 4, Ca5(PO4)3F, Al2O3, Fe2O3, SiO2 . - , , , . , , . , , .
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16.
The reaction of ethynylmagnesium bromide with chloroisopropylgermanes (i-Pr4 - n GeCl/sub> n , n = 1-3) was used to prepare previously unknown ethynylisopropylgermanes i-Pr4 - n Ge(CCH) n (n = 1-3). The reaction of Me3SiCCMgBr with i-PrGeCl3 afforded i-Pr(Me3SiCC)3 - n GeCl n (n = 1, 2). The reaction of the monochloride with BrMdCCH gave i-Pr(HCC)2GeCCSiMe3, while with the dichloride, i-Pr(HCC)·Ge(CSiMe3)2 formed. The latter compounds were obtained by independent synthesis from i-PrGe(CCH)3, EtMgBr, and ClSiMe3. The reaction of (bromomagnesioethynyl)triisopropylgermane with Me3SiCl gave i-Pr3GeCSiMe3.  相似文献   

17.
The thermal properties of coordination compounds of the composition Cu(NCS)2L2 (whereL=pyridine, 2-, 3- and 4-picoline, and 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine) are dealt with. The thermal decomposition of these compounds begins with the release of the ligandL. The compounds with pyridine derivatives containing a methyl substituent at position 2 show a markedly decreased initial decomposition temperature. It was found that X-ray irradiation caused a reduction of the central atom Cu(II) in the coordination compounds under investigation. X-ray electron spectra data showed the stability of the compounds Cu(NCS)2L2 withL=picoline or lutidine having a methyl substituent at position 2 to be distinctly lower in the surface layers. From the given series, the compounds Cu(NCS)2(pyridine)2 and Cu(NCS)2(3,5-lutidine)2 exhibit an analogous course of thermal decomposition in nitrogen atmosphere up to 600°. The stoichiometries of thermal decomposition are discussed.
Zusammenfassung Der Artikel befaßt sich mit den thermischen Eigenschaften von Koordi-nationsverbindungen der Zusammensetzung Cu(NCS)2 L 2 (L= Pyridin, 2-, 3-, 4-Pikolin, 2,3-, 2.4-, 2,5-, 2,6-, 3,4- und 3,5-Lutidin). Die thermische Zersetzung dieser Verbindungen beginnt mit der Abspaltung des LigandenL. Die Verbindungen mit Pyridinderivaten, welche einen Methylsubstituenten in Position 2 im Pyridinring enthalten, zeigen eine deutlich herabgesetzte anfängliche Zersetzungstemperatur. Es wurde gefunden, daß die Röntgenbestrahlung eine Reduktion des zentralen Cu(II)-Atoms bei den untersuchten Koordinationsverbindungen herbeiführte. Die Daten der Röntgen-Elektronenspektren zeigten, daß die Stabilität der Verbindungen Cu(NCS)2L2 mitL=Pikolin oder Lutidin, welche einen Methylsubstituenten in Position 2 enthalten, in den Oberflächenschichten wesentlich geringer ist. Von der gegebenen Reihe der Verbindungen zeigen Cu(NCS)2(Pyridin)2 und Cu(NCS)2(3,5-Lutidin)2 in Stickstoff-Atmosphäre bis zu 600° einen ähnlichen Verlauf der thermischen Zersetzung. Die Stöchiometrie ihrer thermischen Zersetzung wird beschrieben.

Résumé L'article a trait aux propriétés thermiques des composés de coordination de composition Cu(SCN)2L2 (L=pyridine, 2-, 3-, 4-picoline, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-lutidine). La décomposition thermique de ces composés commence avec la libération du ligandL. Les composés avec des dérivés de la pyridine contenant un substituant méthyle en position 2 sur le cycle de la pyridine présentent une température initiale de décomposition qui se trouve abaissée de manière appréciable. On observe que le traitement aux rayons X provoque une réduction de l'atome central Cu(II) dans les composés de coordination étudiés. Les données fournies par les spectres électroniques des rayons X ont montré que la stabilité des composés Cu(SCN)2L2 avecL= picoline ou lutidine, ayant un substituant méthyle en position 2, est nettement plus faible dans les couches superficielles. Dans cette série de composés, Cu(SCN)2 (pyridine)2 et Cu(SCN)2(3,5-lutidine)2 montrent, en atmosphère d'azote, jusqu'à 600°, un processus analogue de décomposition thermique. La stoechiométrie de leur réaction de décomposition thermique est examinée.

Cu(NCS)2L2 L=, 2-, 3-, 4- , 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-. L. 2- . , , Cu(II). , Cu(NCS)2L2 c L= , 2, . Cu(NCS)2 ( )2 Cu(NCS)2 (3,5-)2 600°. .
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18.
The interactions between gaseous sulfur dioxide and nickel oxide at 250° have been investigated by means of temperature-programmed desorption (TPD) and microcalorimetric techniques. Depending on the thermal treatment of the oxide, different NiO samples were prepared containing chemisorbed oxygen species, O1, O2, O3 and O4, with different energies. The calorimetric data indicated that the weakly-bound species O1 is the most reactive of the oxygen forms towards sulfur dioxide. In this case, the TPD curves (m/e=48 andm/e=32) show a new peak at 710°; this may be correlated with the desorption of a sulfur-containing compound, probably NiSO4, created by oxidation of sulfur according to the reaction SIVSVI. The regeneration of the species O1 has been studied as a function of the temperature of oxygen adsorption; the most favourable temperature for the sulfation of nickel oxide appears to be about 400°.
Zusammenfassung Die Wechselwirkung zwischen gasförmigen Schwefeldioxid und Nickeloxid bei 250° wurde mittels temperaturprogrammierter Desorption (TPD) und mikrokalorimetrischer Techniken untersucht. Abhängig von der thermischen Behandlung der Proben wurden verschiedene, die Sauerstoffspecies O1, O2, O3 und O4 mit unterschiedlichen Energien enthaltenden NiO-Proben hergestellt. Die kalorimetrischen Daten weisen darauf hin, dass die schwach gebundene Species O1 gegenüber Schwefeldioxid die reaktivste von diesen Sauerstoffarmen ist. In diesem Falle zeigt die TPD-Kurve (m/e=48 undm/e=32) einen neuen Peak bei 710°; das kann mit der Desorption einer schwefelhaltigen Verbindung, wahrscheinlich NiSO4, erklärt werden, die durch Oxydation von Schwefel entsprechend der Reaktion SIVSVI gebildet wird. Die Regeneration der Species O1 wurde in Abhängigkeit von der Temperatur der Sauerstoffadsorption untersucht; die günstigste Temperatur für die Überführung von Nickeloxid in das Sulfat scheint etwa 400° zu sein.

- 250° . , NiO, O1, O2, O3 O4 . , , O1 - . , - (/=48 32) 710°, , NiSO4 . O1 . , 400°.
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19.
By the method of molecular deposition, ions of CrO 2 2+ VO3+ and MoO 2 2+ were supported on a matrix of amorphous SiO2. Different types of organic ligands were supported subsequently on the surface compounds so formed. The catalytic activity of the samples was studied in the decomposition of comene hydroperoxide.
SiO2 CrO 2 2+ , VO3+, MoO 2 2+ . . .
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20.
A thermal analytical study of Li, Na, K, Rb, Cs, NH4, Mg, Ca, Sr, Ba and Zn dithionates is reported. The decomposition of the dithionate ion is endothermic in the case of the Na, K, Rb, Cs and NH4 salts, but exothermic with Li, Mg, Sr, Ba and Zn. Kinetic parameters have been derived from the TG curves by means of the Coats-Redfern method. The validity of a linear kinetic compensation law is reported for the loss of crystal water and separately for the decomposition of the dithionate ion.
Zusammenfassung Es wird über eine thermoanalytische Untersuchung der Dithionate von Li, Na, K, Rb, Cs, NH4, Mg, Ca, Sr, Ba und Zn berichtet. Die Zersetzung des DithionatIons ist im Falle von Na, K, Rb, Cs und NH4-Salzen endotherm, im Falle von Li, Mg, Sr, Ba und Zn hingegen exotherm. Die kinetischen Parameter wurden aus den TG-Kurven mittels der Coats-Redfern-Methode abgeleitet. Es wird über die Gültigkeit eines linearen kinetischen Kompensationsgesetzes für den Verlust von Kristallwasser berichtet und gesondert für die Zersetzung des Dithionat-Ions.

Résumé On présente les résultats d'une étude par analyse thermique des dithionates de Li, Na, K, Rb, Cs, NH4, Mg, Ca, Sr, Ba et Zn. La décomposition est endothermique dans le cas des sels de Na, K, Rb, Cs et ammonium tandis qu'elle est exothermique dans le cas des sels de Li, Mg, Sr, Ba et Zn. Les paramètres cinétiques sont déduits des courbes TG par la méthode de Coats-Redfern. La validité d'une loi de compensation cinétique linéaire est étudiée pour la perte de l'eau d'hydratation ainsi que pour la décomposition de l'ion dithionate.

Li, Na, K, Rb, Cs,. NH4, Mg, Ca, Sr, Ba Zn. [ Na, K, Rb, Cs NH4 , Li, Mg, Sr, Ba Zn . - . .
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