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Ismat Abu-Isa 《Journal of polymer science. Part A, Polymer chemistry》1970,8(4):961-972
The rate of oxidation of 0.3–0.7 mil films of pure polypropylene is much more rapid than with thicker films. The rate of oxidation increases with the increase in the partial pressure of oxygen and with temperature. The apparent activation energy in oxygen is 22.5 keal/mole. 1,3-Diphenyl-2-propanone added to the polymer acts as an oxidation initiator while p-phenylacetophenone and 4-phenylbenzophenone slightly retard the oxidation. The effects of the additives are more pronounced when the oxidation was carried out in air or at the lower temperatures (90°C) when the oxidation was conducted in pure oxygen. The degree of crystallinity based on the infrared data was found to increase with the degree of oxidation of the polymer. 相似文献
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在水-乙腈混合溶剂中用(NH~4)~2Ce(NO~3)~6氧化烷基蒽. 甲基, 乙基和环丙基蒽经历氧化-水解-氧化-水解-消除-氧化-去质子历程, 得到蒽环氧化产物, 消除烷基(或氢原子)的可能顺序是:H>CH~3>C~2H~5. 当蒽环的1,9-位连着1,2-亚乙基桥时, 却经由氧化-去质子-氧化水解-氧化(或消除)历程, 得到侧链氧化产物. 烷基的本质对多核芳烃的氧化机理有显著的影响. 相似文献
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M. V. Tsarev V. V. Mokrushin A. V. Sten’gach A. I. Tarasova P. G. Berezhko I. K. Kremzukov E. V. Zabavin 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(4):679-683
The oxidation of titanium hydride powder by air oxygen and the influence of oxidation conditions on the degree of oxidation of hydride particles, specific gas content in the powder, and kinetics of its thermal decomposition were studied. The resistometry method was used to determine the effective activation energy of oxidation of titanium hydride by air oxygen. The content of the surface nonconducting phase formed by titanium oxide and oxohydride films under various oxidation conditions was estimated. 相似文献
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二氧化钛薄膜上三氯乙烯光催化氧化反应机理 总被引:3,自引:0,他引:3
研究了二氧化钛薄膜上三氯乙烯(TCE)气相光催化氧化的反应机理. 结果表明,TCE气相光催化氧化反应生成的氯气可引发TCE的连锁反应. 当添加氯气的浓度相同时TCE表面光催化反应的初速率约为光化学反应初速率的2倍,说明连锁反应主要发生在催化剂表面. 氯可吸附在催化剂表面,作为电子的接受体抑制空穴与电子复合,提高TiO2光催化剂的活性. 除了TCE与吸附在催化剂表面的·OH的相互作用及反应产物/中间产物二氯乙酰氯的光催化分解可生成氯气以外,光气在与氯气共存时的光分解也有利于氯的生成. 相似文献
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A. V. Solomonov E. V. Rumyantsev B. A. Kochergin E. V. Antina 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2012,86(7):1048-1052
The results of a comparative study of the oxidation of bilirubin, ascorbic acid, and their mixture in aqueous solutions under the action of air oxygen and hydrogen peroxide are presented. The observed and true rate constants for the oxidation reactions were determined. It was shown that the oxidation of tetrapyrrole pigment occurred under these conditions bypassing the stage of biliverdin formation to monopyrrole products. Simultaneous oxidation of bilirubin and ascorbic acid was shown to be accompanied by the inhibition of ascorbic acid oxidation by bilirubin, whereas ascorbic acid itself activated the oxidation of bilirubin. 相似文献
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L. S. Shibryaeva L. A. Rishina O. V. Shatalova A. V. Krivandin 《Polymer Science Series B》2011,53(11-12):618-625
The mechanism and kinetics of thermal oxidation of metallocene PP are investigated. It is shown that the rate of oxidation of the samples synthesized at a high temperature (40–70°C) is higher than that of the samples synthesized at a low temperature (20 and 30°C). The composition of oxidation products of PP samples; the kinetics of the accumulation of these products; and changes in structural, thermal, and thermophysical parameters during oxidation are analyzed in detail. Our data indicate that the oxidation of low-temperature samples and the oxidation of high-temperature samples obey different mechanisms. The oxidation of low-temperature samples corresponds to the radical-chain process, in which the intramolecular transfer of kinetic chains prevails. High-temperature samples are characterized by the intermolecular transfer of oxidation kinetic chains, which leads to the degradation of macromolecules. It is inferred that the rate and mechanism of thermal oxidation are determined by the microstructure of polymer chains. 相似文献
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Rong-Min Wang Zong-Fan Duan Yu-Feng He Zi-Qiang Lei 《Journal of molecular catalysis. A, Chemical》2006,260(1-2):280-287
A new kind of Co–Na heterodinuclear polymer complex based on Salen Schiff base and crown ether has been successfully prepared by condensation polymerization. Its catalytic behavior for aerobic oxidation of cyclohexene, alkylbenzenes and linear aliphatic olefins was studied in the absence of any solvents or reducing agents under mild conditions. The oxidation of cyclohexene catalyzed by the above catalyst proved to be a simple and efficient method for obtaining 2-cyclohexen-1-one (CO) and 2-cyclohexen-ol (OH) in a high selectivity. Kinetics of the oxidation was also investigated. The results showed that the aerobic oxidation of cyclohexene catalyzed by Salen-crown ether heterodinuclear polymer complex follows a radical chain aerobic oxidation mechanism. This oxidation system is also efficient in the oxidation of alkylbenzenes and linear aliphatic olefins, which afforded corresponding benzylic oxidation products and epoxides, respectively. 相似文献
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Eva González‐Fernández Noemí de‐los‐Santos‐Álvarez María Jesús Lobo‐Castañón Arturo J. Miranda‐Ordieres Paulino Tuñón‐Blanco 《Electroanalysis》2008,20(8):833-839
The electrochemical oxidation of guanosine and xanthosine, which only differ in the presence of an oxygen atom at C2 position instead of an amine group, is studied on pyrolytic graphite electrodes at different electrolysis time scales in solutions of physiological pH. The oxidation products adsorbed on the electrode surface were electrochemical characterized in terms of variation of the formal potential with pH and catalytic activity towards the oxidation of NADH. The results were compared with those previously described for the oxidation of guanosine and adenosine in alkaline solutions. A common oxidation product is described, the oxidized form of 9‐β‐D ‐ribofuranosyluric acid, which is proposed as the point of convergence in the oxidation routes of all three purine nucleosides. 相似文献
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The role of the oxidation state of a platinum polycrystalline surface in the electrocatalytic oxidation of C1 to C4 primary alcohols has been studied by using electrochemical techniques, in situ FTIR spectroscopy and X-ray photoelectron spectroscopy. The results revealed that the oxidation state of the Pt surface plays a key role in the oxidation of primary alcohols, and demonstrated that the oxidation of C1 to C4 primary alcohols on a Pt electrode is controlled by the formation of surface oxides on the Pt electrode at different potentials. It was found that the dependence of the reaction process on the oxidation states of the platinum surface yielded similar features in the cyclic voltammogram for oxidation of different primary alcohols at a Pt electrode. According to the effects in the oxidation of primary alcohols, the surface oxides of platinum may be classified as active and poison species. The Pt surface oxides of higher oxidation states (Pt(OH)3 and PtO2) formed at potentials above 1.0 V (SCE) were identified as poison species, while other lower oxidation states of Pt surface oxides such as PtOH, Pt(OH)2 and PtO may be identified as the possible active species for primary alcohol oxidation. 相似文献
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The oxidation behaviours of pyrrhotite in the form of dense plate, pellet and single particle were compared. In the oxidation of dense plate of FeS, preferential oxidation of iron took place to form a dense oxide layer in the earlier stage of oxidation, and the subsequent oxidation accompanying the evolution of SO2 gas proceeded after the composition of pyrrhotite attained Fe0.9S. In the oxidation of FeS pellet, both the above reactions take place simultaneously because the pellet consists of fine particles. In the oxidation of single particle of small size, ignition of the particle occurred due to the heat of oxidation, and the particle melted in a very short time less than 1 second. 相似文献
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The electrochemical oxidation behaviour at boron doped diamond and glassy carbon electrodes of the sulphur-containing amino acids cysteine and methionine, using cyclic and differential pulse voltammetry over a wide pH range, was compared. The oxidation reactions of these amino acids are irreversible, diffusion-controlled pH dependent processes, and occur in a complex cascade mechanism. The amino acid cysteine undergoes similar three consecutive oxidation reactions at both electrodes. The first step involves the oxidation of the sulfhydryl group with radical formation, that undergoes nucleophilic attack by water to give an intermediate species that is oxidized in the second step to cysteic acid. The oxidation of the sulfhydryl group leads to a disulfide bridge between two similar cysteine moieties forming cysteine. The subsequent oxidation of cystine occurs at a higher potential, due to the strong disulfide bridge covalent bond. The electro-oxidation of methionine at a glassy carbon electrode occurs in two steps, corresponding to the formation of sulfoxide and sulfone, involving the adsorption and protonation/deprotonation of the thiol group, followed by electrochemical oxidation. Methionine undergoes a one-step oxidation reaction at boron doped diamond electrodes due to the negligible adsorption, and the oxidation also leads to the formation of methionine sulfone. 相似文献
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Chockalingam Karunakaran Kaliyaperumal Anandhy Velusamy Ramachandran 《Monatshefte für Chemie / Chemical Monthly》2000,34(2):1025-1029
Upon aging, perborate in glacial acetic acid generates peracetic acid and thus oxidizes S-phenylmercaptoacetic acid rapidly. Perborate dissolved in ethylene glycol, however, does not show the aging effect, and the corresponding oxidation proceeds smoothly. The oxidation is of second order and not acid catalyzed. Boric acid and borate do not influence the oxidation. In the smooth oxidation, is the reactive species. The oxidation of some para-substituted S-phenylmercaptoacetic acids conforms to the Exner relationship, indicating operation of a common mechanism. Also, the oxidation obeys the Hammett equation with a negative reaction constant. However, the oxidation of p-nitro-S-phenylmercaptoacetic acid follows a different kinetic pathway. 相似文献
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The relationships of iron(II) oxidation in water using a new type of aerator based on a disk disperser were studied. The oxidation rate constants and the iron(II) to iron(III) half-conversion time were determined. The iron(II) oxidation in water follows a first-order rate equation. Changes in the water quality parameters depending on the conditions of the iron(II) oxidation were analyzed. 相似文献
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Hiromichi Egami 《Tetrahedron letters》2005,46(36):6049-6052
The mechanism of aerobic oxidation of alcohols using (ON)Ru(salen) complex as catalyst under photo-irradiation was examined through studies of kinetics of the oxidation, kinetic isotope effect in the oxidation, and effect of the ligand structure on the chemoselectivity of the oxidation of primary and secondary alcohols. It was demonstrated that the aerobic oxidation includes an intramolecular hydrogen atom transfer process that is attributed to realization of efficient differentiation of primary and secondary alcohols in the oxidation. 相似文献
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《Colloids and surfaces. A, Physicochemical and engineering aspects》2000,161(3):447-460
The initial steps of the oxidation of galena (PbS) surface with special attention to the oxidation in an aqueous environment were investigated by the X-ray photoelectron spectroscopy method (XPS). Galena monocrystals from two different sources were cleaved and exposed to either air or an aqueous environment. The results show that the presence of organic contamination at the galena surface may exert a dramatic effect on the course of its surface oxidation. In the case of aerial oxidation, the presence of impurities changes the reaction path, suppressing the oxidation of sulfide sulfur to sulfate like species selectively. In the case of aqueous oxidation, the presence of organic contamination at the surface (this contaminants are supposed to be mainly the carboxylic acids and their salts) inhibits the oxidation. Very little oxidation products were found on the galena surface contacted with aqueous solutions at the spontaneously established potential, in accordance with the congruent dissolution-oxidation mechanism. 相似文献
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The dependence of oxidation rate on the sample thickness for high-temperature oxidation of polyphenylene oxide and of polycarbonate has been studied. Sharp maxima in curves of film thickness vs oxidation rate were observed for both polymers. These maxima can be explained assuming that at least two types of mobile low-molecular-weight radicals take part in the high-temperature oxidation reactions. 相似文献
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N. I. Egorenkov D. G. Lin V. A. Bely 《Journal of polymer science. Part A, Polymer chemistry》1975,13(7):1493-1498
Oxidation of polyethylene (PE) melts in contact with metals (Cu, Pb, Au, Al, Zn, Ag) has been studied by infrared spectroscopy and differential thermal analysis (DTA). These metals may be divided into two groups, depending on their activity for oxidizing PE: namely, high-activity metals (Cu, Pb, Ag, Zn) and low-activity metals (Al, Au). During the oxidation of PE in contact with high-activity metals dissolution of the surface layer of metal is observed with accumulation of metal-containing compounds (salts of carboxylic acids) in the bulk of the polymer. With low-activity metals these phenomena are not observed. The rate of oxidation of PE on low-activity metals approaches the oxidation rate of nonmetals (polytetrafluoroethylene and inorganic glass). With certain high-activity metals (Cu, Pb) the process of oxidation is accelerated only in the early stage of oxidation; then the oxidation rate slows down and the oxidation process ceases. PE films separated from metal after being oxidized on it possess chemical memory, i.e., their oxidation rate depends on the nature of the metal with which they had been in contact, and on the duration of the contact oxidation. The effect of salts of carboxylic acids (metal stearates) on the oxidation of PE melts was also studied. Based on the data obtained, it is concluded that the rate of oxidation of PE melts on high-activity metals is controlled by metal-containing compounds which are the products of contact reactions. 相似文献