关于氧化还原平衡处理方法的讨论

氧化还原滴定是分析化学教学的基本内容之一。但氧化还原滴定的理论处理尚不如酸碱与络合滴定理论处理那样完善,有的问题还处于研讨之中。本文拟对氧化还原平衡处理方法中出现的两个新概念——电子活度与半反应平衡常数谈一谈看法,并对氧化还原平衡的图解法提出作者的建议。     

滴定分析的终点误差

终点误差是分析化学教学中滴定分析部分的重要内容之一,国内外分析化学教材对此均有讨论.本文从终点误差的定义出发,根据反应的摩尔比关系,导出计算终点误差的通式,并结合终点时的物料平衡与电荷平衡关系,导出不同类型滴定反应的终点误差计算式,同时讨论该误差公式在酸碱滴定、沉淀滴定、氧化还原滴定和络合滴定中的应用.这些公式较一般的分析化学教材所采用的公式更加容易理解和便于计算,虽然不能包括全部滴定分析误差的计算,但具有较大的普遍性.由于公式是根据反应的摩尔比关系而不是当量关系导出,     

谈谈酸碱滴定教学中新知识的引进

对分析化学酸碱滴定教学中引进酸碱滴定通式的问题进行了讨论。通过实例表明,将酸碱滴定通式引入到教学中,有助于学生更完整正确地把握酸碱滴定的理论。     

基于滴定突跃的计算探讨多元弱酸分步滴定的准确条件

多元弱酸分步滴定的准确条件一直是酸碱滴定中的一个教学难点。基于分布分数的分析指出了当前分析化学教材中有关探讨磷酸分步滴定的某些错误结论,并在此基础上,通过滴定突跃大小的计算,对多元弱酸分步滴定的准确条件进行了探讨分析。结果表明：若人眼判断滴定终点时有±0.2pH的不确定性时,滴定误差控制在0.5%,强碱滴定多元弱酸时,分步滴定的准确条件是：Kai/Ka(i+1)≥105.0;cKai≥10-8.7。     

滴定分析终点误差的通用高效计算策略

终点误差是滴定分析的核心内容之一,现行教材中众多导出公式致使终点误差的计算过于复杂。本文提出了一种通用高效的计算策略,统一了酸碱滴定、配位滴定以及氧化-还原滴定的终点误差计算;此外,还将准确滴定判别统一到终点误差的计算中。各种实例显示,这种策略不要求记忆任何导出公式即可完成计算,而且运算强度低。公式的统一性以及运算的便捷性极大地简化了终点误差的计算,在教学中能够显著减轻学生的记忆和运算负担,提升学习兴趣,从而能够将学习重点放在滴定体系的分析和处理上。本研究作为当前形势下分析化学教学改革的一个尝试,对传统课程内容进行优化,去冗存精,使其简明凝练,重点突出,定量分析的主旨更加明晰。     

存在辅助配位剂时单一金属离子配位滴定曲线的绘制

指出了分析化学教科书[1]在处理辅助配位剂存在时,游离金属离子浓度计算和EDTA滴定剂型体选择的不妥之处,提出了游离金属离子浓度计算方法,并绘制出滴定曲线。     

关于滴定分析计算的教学讨论

本文阐明在分析化学的滴定分析计算中，不采用化学反应的等物质的量规则，不用基本单元表示物质的量浓度的观点。     

论四大滴定理论内容整合与教材改革

提出对四大滴定理论进行整合,统一滴定过程观察量为pM′,删简功能相同或者内容相同的重复概念,围绕滴定反应稳定常数K稳定建立逻辑体系,在数学处理模式上取得一致,从而获得基本理论的统一,同时建议吸收计算机等相关学科的成果来简化并强化分析化学中的计算手段;继承并发展经典的分析化学滴定理论。     

基于Python的沉淀滴定学习软件设计与教学应用

在滴定分析教学中,将现代信息化Python编程语言与沉淀滴定分析法深度融合,设计开发了沉淀滴定学习软件。该软件无需安装和建立复杂的函数或计算方程,用户只需选择和输入相应参数,即可实现沉淀滴定曲线的可视化绘制、滴定可行性判断、化学计量点和滴定突跃范围以及滴定误差的计算等。软件以图形界面形式呈现,设计简洁、操作方便、内容丰富,可选择内置或自定义滴定实例,基本涵盖了沉淀滴定法教学大纲中重要知识点内容,便于教师教学和学生自主学习应用,协同提升教学效果。     

目视滴定的进展

介绍了滴定分析在现代分析化学中的地位，评述了五年来国内目视滴定的新进展。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.