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121.
Aldehyde-2,4-dinitrophenylhydrazones exist as (E)- and (Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the (E)-isomer. However, partial isomerization to the (Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV-visible spectral properties of the isomers differ; the (Z)-isomer exhibiting a 6-10 nm lower absorption maximum compared to the (E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a CC double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The CC double bond at the 3-position migrates to a position of conjugation with the CN double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both (E)- and (Z)-isomers. 相似文献
122.
依据柱相比的热力学定义和反相液相色谱中溶质的计量置换保留理论(the stoichiometric dispheement heory of solute for retention,SDT-R),对反相液相色谱中固定相和流动相性质、温度对柱相比的影响进行了研究。结果表明:固定相的种类和配基的疏水性对柱相比影响较大,而流动相中有机溶剂的种类,特别是脂肪酸作为置换剂时,对柱相比的影响更大,而柱相比受温度的影响较小。此外,通过用27种小分子溶质对柱相比的测定,其logI和Z良好的线性关系,进一步证明柱相比是一个与溶质性质无关的常数。 相似文献
123.
对130℃下1,3 二烯基 1,1,3,3 四甲基二硅氧烷(DVDS)/苯乙烯(St)的溶液环化共聚合动力学进行了研究.根据低转化率(<10%)的共聚物组成及环状结构比例,通过参数估计方法,求得环化率与竞聚率,分别为r1=0102、r2=348、rc=00210、Kc=381mol/L、K′c=0389mol/L,同时得到它们95%置信概率的联合置信区间及其交互影响的联合置信区间.表明DVDS的反应活性较St低,其非环状结构自由基具有较强的分子内环化反应能力;环的位阻效应使环状结构DVDS自由基的活性低于其非环状结构自由基. 相似文献
124.
Study on Bifunctionality of Mo/HZSM-5 Catalysts for Methane Dehydro-Aromatization under Non-oxidative Condition 下载免费PDF全文
Lingling Su Yide Xu Xinhe BaoState Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Zhongshan Road P. O. Box Dalian ChinaManuscript received June revised July 《天然气化学杂志》2002,(Z1)
The optimum Mo/[H~+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by 1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering either the SiO2/Al2O3 ratios or the Mo loading. This implies that a concerted interaction between the Mo species and the Bronsted acid sites probably features the bifunctionality of the Mo/HZSM-5 catalyst. On the other hand, it was found that the driving force for Mo species to move into the HSZM-5 zeolite channels and the interaction between the Mo species and the Bronsted acid sites are closely and proportionably related with the amount of Bronsted acid sites per unit cell. 相似文献
125.
XinZHANG DeHuaHE QiJiangZHANG BoQingXU QiMingZHU 《中国化学快报》2003,14(10):1066-1069
Comparatively high CH3OH selectivity (60.0%) and yield (6.7%) were obtained on MoOx/(LaCoO3 Co3O4) catalysts in selective oxidation of methane to methanol using molecular oxygen as oxidant. The interaction between MoOx and La-Co-oxide modified the molecular structure of molybdenum oxide and the ratio of O^-/O^2- on the catalyst surface, which controlled the catalytic performance of MoOx/(LaCoO3 Co3O4) catalysts. 相似文献
126.
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128.
Classifying wine according to geographical origin via quadrupole-based ICP–mass spectrometry measurements of boron isotope ratios 总被引:1,自引:0,他引:1
The potential of quadrupole-based ICP–MS as a tool for B-isotopic analysis of wines and its usefulness in provenance determinations
were assessed. A precision of 0.1–0.25% RSD (corresponding to a relative standard deviation of the mean of three replicate
measurements of 0.06–0.12%) was sufficient to establish small differences in the B isotope ratios in wines from different
geographical origins. Each sample measurement was bracketed by measurements of a standard and mass bias drift correction made
by interpolation. Sample preparation was kept to a minimum to avoid possible fractionation. Dilution of the wine samples by
a factor of 100 with 0.65% HNO3 was found to reduce matrix-induced mass discrimination substantially. Wines from three wine-producing regions, Stellenbosch,
Robertson, and Swartland, in the Western Cape Province of South Africa, and wines from specific regions in France (Bergerac)
and Italy (Valpolicella) were analyzed by ICP–QMS for their B-isotopic compositions. It was concluded that the 11B/10B ratios can be used to characterize wines from different geographical origins. Average 11B/10B ratios in red wines from South Africa (Stellenbosch), France (Bergerac), and Italy (Valpolicella) were found to differ by
between 0.5 and 1.5%. 相似文献
129.
130.
The viscosity of PEG-modified urethane acrylate (PMUA) showed peculiar behavior in the course of soap-free emulsification. Moreover, the viscosity change with added amounts of water was influenced by the reaction molar ratio of polyethylene glycol (PEG). The rate of increase in viscosity slowed and the ratio of increase in viscosity increased as the reaction molar ratio of PEG increased. This peculiar viscosity behavior was due to the microphase separation between hydrophilic and hydrophobic segments of PMUA, and the orientation of polyoxyethylene groups at O/W interface which influenced droplet size of the soap-free PMUA emulsion. The location of polyoxyethylene groups of this resin at O/W interface was confirmed using the adsorption isotherm measurement of PMUA molecules containing polyoxyethylene groups at water/benzene interface. The microphase separation behavior of PMUA between hydrophilic and hydrophobic segments could apply to the preparation of the PMUA gels containing peculiar structure. PMUA gels were prepared using dioxane (UAG) and the swelling behavior of these gels were compared to that of gels prepared using water (UAHG) in the same medium. In the same medium, the swelling behavior of UAHG gels differed from that of UAG gels because of the difference in the microstructure of gel due to the microphase separation between hydrophilic and hydrophobic segments. This phase separation in the course of gelation in water could be confirmed using contact angle measurement. 相似文献