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71.
The hydrolysis of chromate ion was studied potentiometrically in a concentration cell fitted with hydrogen electrodes by titrating basic NaCl–Na2CrO4 solutions with standardized HCl against a NaOH reference solution. The temperature was varied from 25 to 175°C at 25° intervals at the following ionic strengths (I): 0.1140, 0.2346, 0.5337, 0.9988, 2.940, and 5.239 (NaCl). Depending on the ionic strength, the molality of total chromium was varied from 0.001 to 0.100. The resulting titration curves could be resolved best in terms of three equilibria involving the formation of HCrO
4
–
(aq), Cr2O3– (aq), and CrO3Cl– (aq). The equilibrium quotients for all three reactions were fitted as a function of temperature and ionic strength, and the molal thermodynamic parameters that were computed from these relationships are tabulated at specific ionic strengths over the experimental temperature range. 相似文献
72.
以邻苯二胺为原料合成表征了一类喹喔啉衍生物;1-烷基-3-甲基-2(1H)-喹喔啉-2-酮(1-alkyl-3-methly-2(1H)-quinoxalin-2-one,简称AMQ,其中alky=H、CH3、Et、n-C3H5、n-C5H11、n-C16H33)。用电子轰击电离质谱(EI-MS)和核磁共振谱图(^1H-NMR)鉴定了AMQ,研究了不同取代基对这类化合物EI-MS谱图的影响,分析得到一些裂解规律。结果表明:所有样品谱图中均有芳香化合物的特征CnHn^ 系列峰m/z78,65,52,39和(或)m/z77、76、64、63、51、50、38、37。对于末取代的样品及低级烷烃取代的样品,谱图中的基峰为分子离子峰,对于取代基中碳数大于等于3的样品。谱图中的基峰不是分子离子峰,分子离子峰强度随着碳数的增加而降低。这些样品一般容易发生骨架重排,丢失一分子CO,生成1-烷基-2-甲基苯并哒唑正离子。此外,还讨论了谱图中其它的一些碎片离子峰。这对于研究和指导喹喔啉衍生物 的合成,探讨它们在药效及结构特征与生理活性的关系等方面具有重要的应用价值和理论意义。 相似文献
73.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
74.
75.
The adverse effects of injection solvent strength on microbore packed column SFC band broadening are demonstrated and a solventless injection system that eliminates these effects is introduced. The injection system removes solvent in a GC-like manner using a retention gap and an on-column capillary GC syringe. The analyte is delivered to the analytical column in a solvent-free plug of supercritical fluid mobile phase. 相似文献
76.
HIPS/PP熔融反应共混及其动态力学性质 总被引:2,自引:0,他引:2
研究了高抗冲聚苯乙烯(HIPS)/聚丙烯(PP)共混物在过氧化二异丙苯(DCP)存在下的熔融反应过程及其动态力学性质.HIPS在DCP存在下以聚苯乙烯(PS)的降解为主,伴随着聚丁二烯(PB)的交联和接枝,PP在DCP存在下以降解为主,HIPS/PP在DCP存在下以PP同HIPS的反应接枝为主,这种原位生成的增容剂显著地改善了HIPS/PP两组份间的相容性,其分子运动特征较前两者发生明显变化,PS的Tg下降,PB和PP的Tg升高. 相似文献
77.
H. Pongratz K. K. Mayer W. Wiegrebe 《Monatshefte für Chemie / Chemical Monthly》1997,128(6-7):659-673
Summary N-Butoxy- and N-propoxy-imines derived fromo-,m-, andp-substituted benzaldehydes (X = F, Cl, Br, I) decompose upon electron impact to the respective aldoximes by loss of C
n
H2n
and competitivelyvia 1,5-distonic radical cations by loss of CH2O to 1,3-distonic ions which eliminate H and/or a halogen atom in the course of homolytic aromatic substitution, giving rise to cyclic (M-CH2O-H)+ or (M-CH2O-X
)+ ions.Dedicated with warm regards to Prof. Dr.D. Seebach, Zürich, on the occasion of his 60th birthday 相似文献
78.
A.B. Lugo B.W.H. Artel A. Yoshiga L.F.C.P. Lima D.F. Parra J.R. Bueno S. Liberman M. Farrah W.R. Terariol H. Otaguro 《Radiation Physics and Chemistry》2007,76(11-12):1691-1695
High melt strength polypropylene (HMS-PP) has been recently developed and introduced in the market by the major international producers of polypropylene. Therefore, BRASKEM, the leading Brazilian PP producer, together with EMBRARAD, the leading Brazilian gamma irradiator, and the IPEN (Institute of Nuclear Energy and Research) worked to develop a national technology for the production of HMS-PP. One of the effective approaches to improve melt strength and extensibility is to add chain branches onto polypropylene backbone using gamma radiation. Branching and grafting result from the radical combinations during irradiation process. Crosslinking and main chain scission in the polymer structure are also obtained during this process. In this work, gamma irradiation technique was used to induce chemical changes in commercial polypropylene with two different monomers, Tri-allyl-isocyanurate (TAIC) and Tri-methylolpropane-trimethacrylate (TMPTMA), with concentration ranging from 1.5 to 5.0 mmol/100 g of polypropylene. These samples were irradiated with a 60Co source at dose of 20 kGy. It used two different methods of HMS-PP processing. The crosslinking of modified polymers was studied by measuring gel content melt flow rate and rheological properties like melt strength and drawability. It was observed that the reaction method and the monomer type have influenced the properties. However, the concentration variation of monomer has no effect. 相似文献
79.
Impact Responses of Prismatic Lithium-Ion Battery Based on the Membrane Factor Method北大核心CSCD 下载免费PDF全文
Aimed at the internal short circuit problem due to large deformation of the prismatic lithium-ion battery cell under impact loadings, a simplified battery model was first established. Then the motion equations of velocity and displacement based on the membrane factor method were proposed. With the effects of the face-sheet thickness and the densification region on the normalized final deflection, impact response characteristics of prismatic battery cells were investigated in detail. The results show that, the improved motion equations involving the membrane factor can reflect the dynamic response mechanisms of the prismatic battery cell under impact loadings, and the large deflection under high-speed impact can be predicted. With the increase of the face-sheet thickness, the deflection of the battery cell’s lower part decreases obviously. However, the densification region expands with the face-sheet thickness. The deflection and the densification region of the cell’s lower part both increase with the inner core density of the battery. This proposed impact model provides a theoretical guidance for the multi-functional integrated dynamic design of prismatic battery cells. © 2022 Editorial Office of Applied Mathematics and Mechanics. All rights reserved. 相似文献
80.
通过考虑气候和经济社会因素,将气候因素与函数综合考虑并进行分析,构建“经济气候”模型,分析并得出气候因素对安徽省中药材产业影响程度,利用所构建BP神经网络模型,分析数据,对气象因素对中药材产业的影响结果进行预测。通过分析安徽省气候变化的特点与方向,确定气候因素对中药材产业的影响程度,为中药材产业发展提供一定的数据分析支撑,为有针对性的管理中药材产业提供方法与数据基础,同时对降低严重气象灾害对中药材生产带来的负面作用具有一定的理论与实践意义。 相似文献