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991.
992.
A superoxochromium(III) ion, CraqOO2+, acts as a catalyst for the co-oxidation of alcohols and nitrous acid with molecular oxygen according to the stoichiometry: CH3OH+HNO2+O2→CH2O + NO3− + H2O+H+. The kinetics are second order in [HNO2] and independent of the concentrations of the superoxochromium catalyst, substrate, and O2. The proposed mechanism features the disproportionation of HNO2 to NO and NO2, both of which react rapidly with CraqOO2+. The CraqOO2+/NO reaction generates another equivalent of NO2 and a mole of CraqO2+, the active oxidant. The two-electron oxidation of the alcohol by CraqO2+ produces Craq2+, which reacts rapidly with O2 to regenerate the catalyst, CraqOO2+. The NO2/CraqOO2+ reaction yields the peroxynitrato complex, CraqOONO22+, in a dead-end equilibrium process that has no effect on the catalytic reaction. The disproportionation of NO2 yields the final nitrogen-containing product, NO3−, and regenerates an equivalent of HNO2. Under a fixed set of conditions, the relative catalytic efficiency (CE) of CraqOO2+ decreases as its concentration increases owing to the competition between O2 and CraqOO2+ for the intermediate Craq2+. 相似文献
993.
994.
V. A. Dorokhov L. S. Vasil'ev N. Kyu Khoa N. Kong Hao V. S. Bogdanov 《Russian Chemical Bulletin》1997,46(11):1967-1969
A method for the synthesis of 2,2′-bipyridin-4-one from 4-amino-4-(2-pyridyl)-but-3-en-2-onevia its diphenylboron, chelates was proposed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2071–2073, November, 1997. 相似文献
995.
The stability of hexacyanoferrate(II)-amine(methylamine, ethylenediamine, diethylenetriamine and tetraethylenepentamine) was determined potentiometrically. Species Fe(CN)6(A)H
j
(j–4)
(A=amine) are formed in all the systems investigated, with j=1...n+2 (n=number of aminogroups). Some other complexes Fe(CN)6(A)iHj (with i>1) were also found. The stability of these complexes is fairly high: the full protonated amine species, show for the reaction Fe(CN)6
4- + HnAn+ = Fe(CN)6(A)Hn
(n-4) an equilibrium constant given by logK=0.686+2.10n. Factors affecting the stability are discussed in comparison with similar systems, together with the importance of interferences. 相似文献
996.
Mercury Compounds with Cyancarbanions. II Synthesis and Crystal Structure of Dimercury(I)-bis(1,1,3,3-tetracyanpropenide) The structure of dimercury(I)-bis(1,1,3,3-tetracyanpropenide), Hg2(tcp)2, has been determined by single-crystal X-ray diffraction methods. The crystals are monoclinic, space group P 21/n. The unit cell dimensions are: a = 9.9193(3) Å, b = 5.6912(6) Å, c = 13.3806(4), β = 92.544(4)° and Z = 2. The mercury atoms in the centrosymmetric cation are three-coordinate with Hg? Hg 2.503, Hg? N 2.207, 2.207, 2.560 Å. tcp behaves as a bidentate ligand forming infinite chains running parallel to the a-axis. 相似文献
997.
PEO/PBHE共混体系X射线散射研究 总被引:1,自引:0,他引:1
在聚环氧乙烷(PEO)/聚双酚A羟基醚(PBHE)共混体系中PEO是一个强质子受体,而PBHE是一个强质子给体,两者极易形成氢键,十分有利于形成互容对。笔者研究了PEO/PBHE共混体系的相容性,等温及非等温结晶动力学,本文根据Vonk提出的一维电子密度相关函数,分析了PEO/PBHE的SAXS现象,求得了共混体系的结晶度,片晶层厚度,过渡层厚度及长周期等结构参数。 相似文献
998.
K. Sekine 《Colloid and polymer science》1987,265(12):1054-1060
Dielectric measurements were carried out on aqueous suspensions of poly(methyl methacrylate) microcapsules charged with KCl solutions to examine the KCl permeability of the microcapsules. The specimens exhibited three kinds of dielectric relaxation. Two kinds of dielectric relaxation were observed immediately after washing the specimens with distilled water. These overlapped each other when the specimen was left standing in the measuring cell for a long time. Their relaxation frequencies were affected by the KCl concentration of the suspending medium in which the specimen was kept before washing. Another relaxation was observed distinctly when the spepcimens were washed thoroughly with distilled water. Its relaxation frequency was affected by the KCl concentration of the charged solution. These results were explained by assuming that the specimens were mixtures of KCl-permeable and KCl-impermeable capsules. The theoretical analysis procedure was devised in the light of dielectric theory of interfacial polarization to estimate the parameters which characterize the structure of the specimens. 相似文献
999.
Javad Zolgharnein Fariborz Riahii Saeid Amani 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(1-2):13-17
The complexation of La(III), Ce(III), Pr(III) and Er(III) with 18-crown-6(18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DCY18C6) anddibenzopyridino-18-crown-6 (DBPY18C6) has been studied in dimethylsulfoxide(DMSO) by means of a competitive spectrophotometric method using murexide asa metal ion indicator. The formation constants of the 1 : 1 complexeswere found tovary in the order La(III) > Ce(III) > Pr(III) > Er(III). It was foundthat the structure influences the formation and stability of the resultingcomplexes. The effects ofvarious parameters on complexation are discussed. The order of the stabilityconstants of each lanthanide ion with these macrocycles are18C6 > DC18C6 > DB18C6 > DBPY18C6. 相似文献
1000.
用量子化学从头算方法(HF/6-31G)和密度泛函理论(DFT)的B3LYP方法,以6-31G标准基组加一个极化函数,对(ClAlNH)n(n=1-10)簇合物的几何构型,电子结构和红外光谱进行了优化,并讨论了聚合反应(ClAlNH)m→(ClAlNH)n的热力学效应,结果表明,(ClAlNH)n系列簇合物的基态稳定结构为Cs(n=1),D2h(n=2),D3h(n=3),Td(n=4),Cs(n=5),D3d(n=6),Cs(n=7),S4(n=8),D3h(n=9),C2h(n=10,n=2,4,6,8,10等偶数对应的(ClAlNH)n簇化合物的结构比n等于奇数量更稳定。 相似文献