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91.
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
92.
研制了酸度在线检测装置,并应用于溶液酸度在线检测,溶液酸度在线检测装置,设有防污过滤器,自动采样器,蠕动泵,小型管道pH传感器和控制电路等,其特点为防污除油,随机自动采样,定时检测,全部管道化,可单独使用和计算机控制系统联网,适用于溶液酸在线分析,测定精度〈pH0.05。 相似文献
93.
94.
Crude extracellular invertase fromSclerotium rolfsii, when coupled to glutaraldehyde activated Indion 48-R, retained 70–80% activity of the soluble enzyme. Immobilization resulted
in a decrease in the pH and temperature optima but it increased the temperature stability. Km and Vmax also increased as a result of immobilization. Both soluble and immobilized invertase showed inhibition at high substrate
concentrations. The bound enzyme showed excellent stability to repeated use and retained approx 90% of its initial activity
after 8 cycles of use. 相似文献
95.
以常见的阴、阳离子的检验为例,研究了如何实施基于标准的教学。校本教材的开发为标准、教材、教学、评价的一致性提供保障;以学生应知的和能做的驱动课堂活动;根据达成标准应有怎样的质量表现,试卷编制先于教学设计。课堂上,“教”“学”双方都明确学习目标,教师提供多种策略来满足学生多样的学习需要,如提供工具,搭建脚手架,并以“微”研究性学习的方式展开教学,给学生提供了充分的进步空间。 相似文献
96.
We prove two new upper bounds on the size of binary codes with a minimum distance of three, namelyA(10, 3)76 andA(11, 3)152. 相似文献
97.
Tamás F. Móri 《Journal of Theoretical Probability》1995,8(1):139-164
Considering an infinite string of i.i.d. random letters drawn from a finite alphabet we define the cover timeW
n
as the number of random letters needed until each pattern of lenghtn appears at least once as a substring. Sharp weak and a.s. limit results onW
n
are known in the symmetric case, i.e., when the random letters are uniformly distributed over the alphabet. In this paper we determine the limit distribution ofW
n
in the nonsymmetric case asn. Generalizations in terms of point processes are also proved.Dedicated to Endre Csáki on his 60th birthday. 相似文献
98.
Alexander Koldobsky 《Journal of Theoretical Probability》1994,7(1):135-145
Let μ be a measure in a Banach spaceE, f be an even function onR. We consider the potentialg(a)=f E f(‖x?a‖)dμ(x). The question is as follows: For whichf does the potentialg determine μ uniquely? In this article we give answers in the cases whereE=l ∞ n and wheref(t)=|t| p andE is a finite dimensional Banach space with symmetric analytic norm. Calculating the Fourier transform of the functionf(‖x‖ ∞) we give a new proof of the J. Misiewicz's result that the functionf(‖x‖ ∞) is positive definite only iff is a constant function. 相似文献
99.
随着以太网通信技术的发展,局域网子网间的通信业务增长迅速,而适用于子网间数据通信的传统路由器因为其转发速度慢、用户配置复杂等缺点,难以满足当前大量跨子网以及虚拟局域网之间通信数据量的需求。基于片上系统(System-on-Chip, SoC)平台FMQL45T900型号的FPGA芯片,采用VHDL硬件描述语言,自主研发了12端口的千兆以太网三层交换功能,并已在相应的硬件平台上进行了功能验证和性能测试。实验结果表明,基于固定长度链表的哈希查找方式实现简单、查找高效、复杂度低,该研究成果可在某些需要进行数据灵活交换的特殊的场景下进行应用。 相似文献
100.
Chunliu Xu Weibo Hua Qinghua Zhang Yuan Liu Rongbin Dang Ruijuan Xiao Jin Wang Zhao Chen Feixiang Ding Xiaodong Guo Chao Yang Liangrong Yang Junmei Zhao Yong-Sheng Hu 《Advanced functional materials》2023,33(33):2302810
Na superionic conductor of Na3MnTi(PO4)3 only containing high earth-abundance elements is regarded as one of the most promising cathodes for the applicable Na-ion batteries due to its desirable cycling stability and high safety. However, the voltage hysteresis caused by Mn2+ ions resided in Na+ vacancies has led to significant capacity loss associated with Mn reaction centers between 2.5–4.2 V. Herein, the sodium excess strategy based on charge compensation is applied to suppress the undesirable voltage hysteresis, thereby achieving sufficient utilization of the Mn2+/Mn3+ and Mn3+/Mn4+ redox couples. These findings indicate that the sodium excess Na3.5MnTi0.5Ti0.5(PO4)3 cathode with Ti4+ reduction has a lowest Mn2+ occupation on the Na+ vacancies in its initial composition, which can improve the kinetics properties, finally contributing to a suppressed voltage hysteresis. Based on these findings, it is further applied the sodium excess route on a Mn-richer phosphate cathode, which enables the suppressed voltage hysteresis and more reversible capacity. Consequently, this developed Na3.6Mn1.15Ti0.85(PO4)3 cathode achieved a high energy density over 380 Wh kg−1 (based on active substance mass of cathode) in full-cell configurations, which is not only superior to most of the phosphate cathodes, but also delivers more application potential than the typical oxides cathodes for Na-ion batteries. 相似文献