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1.
Generation of gradientless conditions by the pulsation method with variable reciprocating gas flow method through the isothermal catalyst bed is suggested as one of the trends in the further development of external circulation flow systems. The conditions ensuring continuous stirring have been established. Flowcirculation and pulsation methods have been tested under similar conditions.
- - . , , - .
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2.
The kinetics of CCl3 radical addition to 1-hexene in CCl3Br and CCl4 media has been studied. The rate constant of CCl3 addition to the double bond is shown to be independent of the solvent. The ratios between the rate constants of transfer and allyl chain termination for the alkyl and polychloroalkyl radicals have been estimated by competition methods. Activation parameters for the calculated rate constants are given.
CCl3- 1- CCCl3Br CCl4. , . . .
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3.
4,4-bismaleimidophenyl methane (BM) and 3,3-bismaleimidophenyl sulfone (BS) were blended in solution using weight ratios 31 (MS31), 21 (MS21), 11 (MS11), 12 (MS12) and 13 (MS13). Chain extended bismaleimide resins were also prepared by treating BS/BM with 4,4-diaminodiphenyl ether in molar ratios of 10.3 (BM-E and BS-E resins). These resins were also blended with bismaleimides and the curing characteristics were evaluated by differential scanning calorimetry. Increase in BM content in BMBS blends or increase in chain extended bismaleimide content in BM-EBS or BS-E BM blends resulted in a reduction of melting and curing temperatures. Indication about the extent of cross-linking was obtained from solubility measurements (in DMF) of isothermally cured resins (180 °C, lh and 220 °C, lh in an air oven). Thermogravimetric analysis of samples isothermally cured at 180 °C and 220 °C (lh each) was carried out in nitrogen atmosphere. Improvement in thermal stability of chain extended bismaleimides was observed on blending.
Zusammenfassung 4,4-Bismalimidophenyl-methan (BM) und 3,3-Bismalimidophenyl-sulfon (BS) wurden in Lösung in den Gewichtsverhältnissen 31 (MS31), 21 (MS21), 11 (MS11), 12 (MS12) und 13 (MS13) gemischt. Auch kettenpolymerisierten Bismalimid-Harze wurden durch Behandlung von BS/BM mit Diaminodiphenylether im Molverhältnis 10,3 dargestellt (BM-E- und BS-E-Harze). Die Kennwerte der Aushärtung von Mischungen dieser Harze mit den Bismalimiden wurden mittels DSC ermittelt. Eine Erhöhung des BM-Gehaltes in den BM BS-Mischungen oder des Gehaltes der BM-E BS oder BS-E-Mischungen an kettenpolymerisierten Bismalimiden führt zu einer Erniedrigung der Schmelz- und Aushärtetemperaturen. Hinweise über den Vernetzungsgrad wurden aus Löslichkeitsmessungen (in DMF) von Isotherm (je 1 Stunde bei 180 und 220 °C in Luft) gehärteten Harzen erhalten. Die thermogravimetrische Analyse der Isotherm bei 180 bzw. 220 °C 1 Stunde ausgehärteten Proben wurde in Stickstoffatmosphäre ausgeführt. Die thermische Stabilität der Bismalimide wird durch Verschneiden verbessert.

4,4-- () 3,3-- () 31 (MC 31), 21 (MC 21), 11 (MC 11), 12 (MC 12) 13 (MC13). - / 4,4- 10,3 ( - C-). - . - - - - , . ( 1 180 220°) . . - .


The financial assistance provided by Department of Science and Technology is gratefully acknowledged.  相似文献   

4.
The thermal behaviour of three gagates (Bulgaria) was investigated by DTA and TG. The characteristic endo- and exoeffects and the sequence of the thermal stabilities are established.
Zusammenfassung Das thermochemische Verhalten von drei Gagaten (Bulgarien) wurde mittels DTA und TG untersucht. Die charakteristischen endo- und exothermen Effekte und die Reihenfolge der thermischen Stabilitäten wurden ermittelt.

(). - .
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5.
The micellar effet of sodium dodecyl sulfate (SDS) on the initial stages of the reaction between (1) Fe(II) and p-benzoquinone, and (2) Fe(III) and hydroquinone have been investigated. In the former case acceleration was observed, the rate-[surfactant] profile showing a maximum. SDS has an inhibitory effect on the latter reaction. Kinetic analysis has been carried out using Berezin's approach.
() 1) Fe(II) 2) Fe(III) . - . . , .
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6.
Heat treatment of porous glasses results in a migration of boron to the surface changing surface acidity. The surface acidity of thermally modified porous glasses was characterized by NH3 desorption and the catalytic activity for conversion of alcohols was investigated.
, . NH3, .
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7.
Résumé Sous azote ou sous vide, le sulfite ferreux anhydre se décompose vers 210° en magnétite, pyrite et dioxyde de soufre. Concurremment une réaction de dismutation intervient avec formation de FeSO4, Fe3O4 et FeS2. Lorsque la température atteint 320°, la pyrite et le sulfate réagissent ensemble pour donner Fe1–xS, Fe3O4 et SO2. Au-delà de 370° le sulfure ferreux non-stchiométrique commence à réagir à son tour avec le sulfate restant pour former de la magnetite et du dioxyde de soufre.
In nitrogen or under vacuum, anhydrous iron(II) sulfite decomposes near 210° to magnetite, pyrite and sulfur dioxide. A parallel disproportionation reaction occurs with formation of FeSO4, Fe3O4 and FeS2. When the temperature reaches 320°, pyrite and sulfate react together to give Fe1–xS, Fe3O4 and SO2. Above 370° the non-stoichiometric ferrous sulfide begins to react with the remaining sulfate to give magnetite and sulfur dioxide.

Zusammenfassung Unter Stickstoff oder im Vakuum zersetzt sich das wasserfreie Eisen(II)-sulfit in der Nähe von 210 °C zu Magnetit, Pyrit und Schwefeldioxid. Parallel hierzu findet eine Disproportionierung unter Bildung von FeSO4, Fe3O4 und FeS2 statt. Wenn die Temperatur 320 °C erreicht, reagieren Pyrit und Sulfat unter Bildung von Fe1–xS, Fe3O4 und SO2 Oberhalb von 370 °C beginnt das nichtstöchiometrische Eisensulfit seinerseits mit dem restlichen Sulfat zu reagieren um Magnetit und Schwefeldioxid zu ergeben.

(II) 210° , . FeSO4, Fe3O4 FeS2. 320°, , Fe1–xS, Fe3O4 SO2. 370° .
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8.
Zusammenfassung Das System KNbO3–Nb2O5 wurde mit thermoanalytischen, dilatometrischen und röntgenographischen Methoden neu untersucht. Acht ternäre Verbindungen werden im Bereich von 0–50 Mol-% K2O gefunden. Nur K4Nb6O17 schmilzt kongruent, alle anderen zersetzen sich peritektisch. Bei den beiden niobreichaten ternären Verbindungen handelt es sich um Hochtemperaturphasen, die sich erst oberhalb 1273 bzw. 1551 K bilden. Drei der acht Verbindungen wandeln sich mit steigender Temperatur in ihre Hochtemperaturmodifikation um.
The KNbO3-Nb2O5 system was studied by thermal analysis, dilatometry and X-ray techniques. Eight ternary compounds were found in the range from 0 to 50 mol% K2O. Only K4Nb6O7 was found to melt congruently, the other compounds decomposed peritectically. For the two ternary compounds with the highest percentage of niobium high-temperature phases were observed which were formed only above 1273 and 1551°, respectively. Three of the compounds studied transformed into their high temperature modifications on heating.

, $ KN3-Nb2O5. 0 50 % . , K4Nb6O7 , $ . $ $ 1273 1551°. $ $ .
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9.
It has been established that zeolites containing Pd and Cu ions catalyze the vapor phase oxidation of methylpyridines. In oxidation of 2-methylpyridine on PdCuNa-mordenite at 375 °C the yield of 2-pyridinecarbaldehyde is 40 % of its theoretical values.
, , Pd Cu, . 2- PdCuNa- 2- 375°C 40% .
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10.
The kinetics of phosphate sorption on Amberlite IRA-400 has been studied as a function of temperature, nature of counterions, at two different concentrations. The film and particle diffusion coefficients and the activation parameters of the process are calculated.
IRA-400 , . .
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11.
IR spectroscopy has been used to follow the transformation at different temperatures of piperidine chemisorbed on oxidic or sulfided Ni–W/Al2O3 catalysts. Formation of an intermediate species, possibly tetrahydropyridine, and pyridine is evidenced. Their formation temperature on the sulfided samples accounts for the catalyst activity in pyridine hydrogenation under H2 pressure.
- , Ni–W/Al2O3, . , , . .


This work was supported by the Groupement scientifique Hydrotraitement catalytique (CNRS-IFP, TOTAL. ELF).  相似文献   

12.
The kinetics of oxidation of diethyl and triethylamine with molecular oxygen catalyzed by RuIII (EDTA-H) (H2O) complex has been studied at different temperatures (25–45 °C at pH 2.0 (=0.5 M KCl) as a function of amine concentration. The thermodynamic (G0, H0 and S0) and the activation parameters (H and S) for the reaction were computed.
- , RuIII (EDTA-H) (H2O) (25–45°C) pH=2 (=0,5 M KCI) . (G0, H0 S0), (H S).
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13.
Catalytic properties of a mechanical mixture of SiO2-iminodiacetatechromium(III)+V2O5/SiO2 have been studied. A synergetic effect in the combined catalytic oxidation-epoxidation of cyclohexene, observed at about 40 wt.% V2O5, is due to the autocatalytic character of the combined process.
Cr(III), - . 40% . - . , .
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14.
The combustibilities ofcis-1,4-polyisoprene and its peroxide and sulphur vulcanizates have been investigated by means of the oxygen index method. The temperature distribution in the sample and the molecular weight of the liquid products formed as a result of elastomer destruction in the combustion zone have been measured. It has been found that the combustibility ofcis- 1,4-polyisoprene diminishes as its cross-link density increases. This effect is much stronger for sulphur than for peroxide vulcanizates. The investigations lead to the conclusion that a mechanism of network degradation and volatile sulphur compounds penetrating to the flame are responsible for this difference.
Zusammenfassung Die Brennbarkeit des unvernetztencis-1,4-Polyisoprens und seiner Peroxid- und Schwefelvulkanisate wurde mit der Sauerstoffindexmethode untersucht. Messungen der Temperaturverteilung im Prüfling wurden ebenfalls ausgeführt und das Molekulargewicht der infolge der Zersetzung der Elastomere in der Verbrennungszone entstehenden flüssigen Produkte mit der Methode der dynamischen Osmometrie bestimmt. Es wurde festgestellt, daß die Brennbarkeit des cis-1,4-Polyisoprens mit zunehmender Vernetzungsdichte abnimmt, und zwar viel ausgeprägter im Falle der Schwefel- als im Falle der Peroxidvulkanisate. Es wurde gefolgert, daß flüchtige, in die Flamme gelangende Schwefelverbindungen als Verbrennungsinhibitoren wirken.

-1,4- . , . , -1,4- . . , .
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15.
Based on TPR investigations of oxidized 5 % Rh/ZrO2 catalyst a substantial effect of rhodium both on increase in degree of surface reduction of the support and lowering of reduction temperature range as compared to the support alone was observed. With growing reoxidation temperature, a gradual increase in degree of oxidation of rhodium takes place until Rh2O3 is formed at temperature about 770 K. Simultaneously, the support surface is gradually reoxidized until a prilmary state is reporduced at 720–779 K.
5% Rh/ZrO2, , . , Rh2O3 770 . , , 720–770 .
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16.
The doping of MnO2 with small quantities of Bi2O3 results in an increase of the surface oxygen bond energy. Accordingly, the values of the specific catalytic activity and selectivity to nitrous oxide are lower for the doped catalyst than for pure MnO2. The mechanism of low temperature ammonia oxidation is the same on both catalysts.
Bi2O3 MnO2 . , , MnO2. .
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17.
The hydrated rare earth orthophosphates LnPO4 ·xH2O (Ln=La-Dy) contain zeolitic water in the structural channels, which is released reversibly up to 300°. The thermal stabilities of the hydrates depend upon the nature of the Ln atom. The dehydration temperature decreases with decreasing ionic radiusr of Ln3+, according to the general equation=(r–a)/b (where is the DSC and/or DTG dehydration peak temperature, anda andb are empirical constants depending on the experimental conditions).The contracting-area rate equation was valid for linearization of the isothermal vs. time plots in the range 0; 0.65. Kinetic values ofE, A, H + and S+ were calculated and the kinetic stabilities of the hydrates are discussed.
Zusammenfassung Die hydratisierten Seltenerdiphosphate LnPO4·xH2O (Ln=La bis Dy) enthalten in Kanälen ihrer Struktur zeolithisches Wasser, das reversibel bis 300 °C abgegeben wird. Die thermische Stabilität der Hydrate hängt von der Natur des Ln ab. Die Entwässerungstemperatur sinkt mit abnehmendem Ionenradiusr der Ln3+-Ionen gemäss:=(r–a)/b (a undb sind empirische Konstanten, die von den experimentellen Bedingungen abhängen). Die isotherme Entwässerung lässt sich im Umsatzbereich 0 0,65 mit der Gleichung für kontrahierende Fläche (zweidimensionale Phasengrenzreaktion) beschreiben. Die kinetischen Grössen AktivierungsenergieE, -enthalpieH *, und -entropieS * wurden berechnet und die kinetische Stabilität der Hydrate wird diskutiert.

LnPO4·xH2O (Ln=La-Dy) , 300°. . r =(r-)/b, 9 — , a b — , . — <0; 0,65>. , , * S * .
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18.
The reactivity of allyl (o-halophenyl) ethers with zerovalent nickel complexes, with triphenylphosphine and pyridine as ligands, leading to benzo[b]furan derivatives has been checked. Cyclization products were not isolated, but deallylation, substitution, reduction and rearrangement products were obtained in low to moderate yields. Mechanisms are proposed to explain the formation of these side products.
-(o-) , , [b] . , , , , . .
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19.
The reaction of hydrogen atoms with carbon monoxide has been studied in discharge flow systems with a new method of detection of atoms. The results obtained with tubular and jet stirred open reactors agree with those of other authors working in transient conditions and with more sophisticated techniques.
. , , , .
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20.
An investigation of the thermal decomposition of fish oils and motor lubricating oils resulted in the elaboration of a new method, which, by utilizing the relationship between the temperatures of mass losses and the changes in the cnemical composition due to the oxidative and hydrolytic decomposition of fish oils and to the processes occuring in lubricating oils in the course of their service in the oils system of combustion engines, allows estimations of the physicochemical properties of these oils.
Zusammenfassung In Zusammenhang mit der Ausarbeitung einer neuen Methode, die die Abschätzung der physikalisch-chemischen Eigenschaften von Fischölen und Motorschmierölen ermöglicht, wurde eine Untersuchung über die thermische Zersetzung dieser Öle durchgeführt. Als Grundlage dafür diente der Zusammenhang zwischen der Masseverlusttemperatur und der mit der oxidativen bzw. hydrolytischen Zersetzung von Fischölen und den Alterungsprozessen von Motorschmierölen in Verbrennungsmotoren in Verbindung stehenden Veränderung der chemischen Zusammensetzung.

, - , , , , .
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