共查询到20条相似文献,搜索用时 0 毫秒
1.
Timofeeva M. N. Matrosova M. M. Maksimov G. M. Likholobov V. A. Golovin A. V. Maksimovskaya R. I. Paukshtis E. A. 《Kinetics and Catalysis》2001,42(6):791-795
The esterification reaction of n-butanol with acetic acid ([BuOH] : [HOAc] = 1 : 15 mol/mol; 55°C, 5% H2O) was studied in the presence of tungsten heteropoly acids of the Keggin (H3PW12O40, H4SiW12O40, H5PW11TiO40, H5PW11ZrO40, and H3PW11ThO39) and Dawson structure (-H6P2W18O62, H6P2W21O71(H2O)3, H6As2W21O69(H2O), and H21B3W39O132). The reaction orders with respect to H6P2W21O71(H2O)3, H3PW12O40, and H6P2W18O69are equal to 0.78, 1.00, and 0.97, respectively. It was found that the reaction rate depends on the acidity, as well as on the structure and composition of heteropoly acids. The H21B3W39O132heteropoly acid is most active, whereas the Keggin-structure heteropoly acids exhibit the lowest activities. Of the Keggin structure heteropoly acids, H5PW11ZrO40exhibits the highest activity because of the presence of a Lewis acid site in its structure. 相似文献
2.
稀土杂多酸性质及催化作用的研究 总被引:3,自引:1,他引:3
稀土硅钨酸钾盐,R.D.Peacok等早已于1971年合成过,但对其性质报导甚少,尚未见应用。我们用自制的稀土杂多酸,测定了热稳定性、红外吸收谱及X射线衍射谱;探索了在催化中的应用,发现在甲醇转化为低级烃类的反应中,稀土硅钨酸有良好的催化活性,并展现出三峰的规律性。 相似文献
3.
4.
烟碱-磷钼杂多酸缔合微粒体系的光谱研究及分析应用 总被引:1,自引:0,他引:1
采用分光光度法和共振散射光谱法研究了小烟碱一磷钼杂多酸缔合微粒体系.在波长300~800nm范围内,波长愈短缔合微粒体系的吸光度值愈大,在400nm处的吸光度与烟碱浓度在0.50-50.0μg/mL范围成良好线性关系,检出限(3σ)为0.1μg/mL.据此建立了一个测定烟草中烟碱含量的分光光度法.该法灵敏、简便、快速、准确、重复性好,平均回收率为99%~103%,相对标准偏差RSD为0.9%~1.3%.共振散射光谱研究结果表明,该体系存在烟碱-磷钼杂多酸缔合微粒,该微粒在420nm处存在共振散射效应. 相似文献
5.
6.
M. N. Timofeeva G. M. Maksimov V. A. Utkin V. A. Likholobov 《Kinetics and Catalysis》2000,41(6):767-770
The reactions of phenol coupling with ketones MeCOR (R = CH3, C2H5, C3H7, and C4H9) are studied in the presence of heteropoly acids with different structures and compositions in toluene solutions ([PhOH]/[MeCOR] = (2–8)/1 mol/mol; 50–70°C) with thioglycolic acid added as a promoter. The reaction rate depends on ketone and heteropoly acid, and the yield of bisphenols is as high as 24–72%. The reaction orders are 0.68, 0.77, and 0.97 with respect to H6P2W21O71, H3PW12O40, and H4SiW12O40, respectively, and the activation energies are 25.1, 21.0, and 20.6 kcal/mol, respectively. Heteropoly acids of the Dawson structure exhibited the highest activity. 相似文献
7.
8.
9.
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
10.
Chockalingam Karunakaran Kaliyaperumal Anandhy Velusamy Ramachandran 《Monatshefte für Chemie / Chemical Monthly》2000,131(10):1025-1029
Summary. 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.
Received March 15, 2000. Accepted (revised) May 3, 2000 相似文献
11.
Synthesis of Pharmaceutical Intermediates by Toluene Benzylation over Heteropoly Acids on Different Support 下载免费PDF全文
V. V. Bokade G.D. Yadav 《天然气化学杂志》2007,16(2):186-192
Selective formation of pharmaceutical intermediates like diphenylmethane, dimethyl- diphenylmethane, benzyl toluene and benzoic acid by liquid phase, toluene benzylation with benzyl chloride as a benzylating agent, was systematically studied over plane clay (K-10, montmorillonite), plane H-Beta, plane MFI structured titanosilicate (TS-1) and heteropoly acids [HPA, namely dodeca-tungstophosphoric acid [H3PO4.12WO3.xH2O] (TPA), dodeca-molybdo phosphoric acid ammonium salt hydrate [H12Mo12N3O40P aq] (DMAA), sodium tungstate hydrated purified [Na12WO4.2H2O] (STH)] supported on clay, H-beta and TS-1. The 20%TPA/Clay, 30%TPA/H-Beta and 30%TPA/TS-l, were observed to be the best catalyst samples over plane clay, plane H-Beta and plane TS-1. The catalyst samples are compared with respect to benzyl chloride conversion and selectivities for diphenylmethane, dimethyl-diphenylmethane, benzyl toluene and benzoic acid. The reaction follows the pseudo-first order rate power law model. The apparent rate constants are calculated and compared with the reported ones. 相似文献
12.
13.
14.
醋酸胶片的片基材料醋酸纤维素酯水解产生的"醋酸综合症"是影像部门保存醋酸胶片过程中遇到的最大技术难题之一,目前还没有较好的治理方法,其在降解过程中释放出的醋酸严重影响胶片的耐久性,关于其物理性能变化及相关性的研究较少.本文通过模拟密闭环境中醋酸浓度的累积实验,系统地分析了醋酸在胶片降解过程中对胶片物理性能的影响.实验结果表明,醋酸环境会加速胶片的降解,且随着醋酸浓度的增加,胶片扭曲变形程度增加,胶片的降解程度(酸度)增加;抗张强度减弱,但耐折度增加;含湿量和胶片乳剂层面的亲水性增加,同时胶片的热稳定性变差. 相似文献
15.
A facile access to trimethylsilyl acetic acid is described. The method involves the preparation of the corresponding trimethylsilyl ester in fairly good yield (70%). 相似文献
16.
17.
18.
19.
Dynamic protonation equilibria in water of one 4‐methylimidazole molecule as well as for pairs and groups consisting of 4‐methylimidazole, acetic acid and bridging water molecules are studied using Q‐HOP molecular dynamics simulation. We find a qualitatively different protonation behavior of 4‐methylimidazole compared to that of acetic acid. On one hand, deprotonated, neutral 4‐methylimidazole cannot as easily attract a freely diffusing extra proton from solution. Once the proton is bound, however, it remains tightly bound on a time scale of tens of nanoseconds. In a linear chain composed of acetic acid, a separating water molecule and 4‐methylimidazole, an excess proton is equally shared between 4‐methylimidazole and water. When a water molecule is linearly placed between two acetic acid molecules, the excess proton is always found on the central water. On the other hand, an excess proton in a 4‐methylimidazole‐water‐4‐methylimidazole chain is always localized on one of the two 4‐methylimidazoles. These findings are of interest to the discussion of proton transfer along chains of amino acids and water molecules in biomolecules. 相似文献
20.
Kinetics and Catalysis - Changes in the values of specific conductance χ of the solutions of high-vanadium Mо?V?Р heteropoly acids (HPA-х) in redox processes are... 相似文献