铁吸氧腐蚀的实验创新

铁的吸氧腐蚀一直是化学教学中的一个难点,对正极氧气参与的电极反应学生难以理解和接受。按照人教版《化学反应原理》中铁的吸氧腐蚀实验的方案进行实验[1],5~8分钟才有明显现象;其次该实验说服力也不够强,导管中液面上升不能证明     

金属电化学腐蚀的实验探究

金属的电化学腐蚀是高二化学新教材(人教版)“原电池原理及其应用”一节的教学难点,教师按照传统的教学方法向学生讲清楚钢铁在潮湿空气里形成原电池时正、负极发生的反应并不容易。笔者在教学实践中采用实验探究式教学,把课堂教学与研究性学习结合起来,引导学生通过自主活动来探究金属电化学腐蚀的一些规律,既有助于理解、巩固化学知识,又能培养学生的实践能力和探究精神。     

肉桂醛壳聚糖席夫碱对N80钢的缓蚀行为评价

以肉桂醛改性壳聚糖制备了肉桂醛壳聚糖席夫碱(CACS),利用红外光谱、热重实验对其结构表征。利用失重实验、电化学极化曲线评价了其在1 mol/L氨基磺酸中对N80钢的缓蚀性能。结果表明在1 mol/L氨基磺酸中CACS能有效的抑制酸液对N80钢的腐蚀,当其浓度为1000 mg/L时,缓蚀率高达98.09%,属于混合抑制型缓蚀剂。吸附模型分析可知CACS在N80表面的吸附与Langmuir吸附模型相符,存在化学与物理两种吸附形式,且CACS加入后提高了腐蚀过程的活化能,减慢了腐蚀反应速率,抑制了N80钢的腐蚀。     

铜电极在弱碱性介质中腐蚀行为的研究

应用循环伏安法和现场椭圆偏光法研究了弱碱性介质中铜的腐蚀、钝化过程,并用二组分有效介质模型对光学实验结果进行了拟合。结果表明金属铜在腐蚀达到稳态时其表面氧化膜具有一定的组成和厚度;反应生成的CuO比Cu2O更为致密,因而对基体具有更好的保护作用;CuO的阴极还原过程可能会涉及到还原中间产物Cu^+的岐化反应,该岐化反应的进行有助于铜耐蚀性的提高;CuO的还原可以在小于-0.45V(vs.SCE)的电位范围内与Cu2O的还原同时进行,椭圆偏光实验不仅与电化学和光电化学实验的结果一致,还能定量地确定膜的厚度、折射率等性质;并根据有效介质模型,可以计算得到不同时刻电极表面膜组成的改变;从而为研究电极反应机理提供新的证据。     

基于原理解读的铁吸氧腐蚀实验再设计

由教材中吸氧腐蚀原理的解读引发思考, 对相关铁吸氧腐蚀实验再研究, 从溶液中的氧气参与吸氧腐蚀反应的角度设计吸氧腐蚀实验器, 用数字化实验技术中的溶解氧传感器进行实验, 能直观形象地看到溶解氧参与反应, 且有电流产生, 还探究了氯化钠溶液进行实验时的最佳浓度。     

卤化物对铜铝置换反应速率的影响研究*

从定性和定量角度探究了卤化盐对金属置换反应的催化作用,实验结果表明:卤族元素均有催化作用,Cl^-催化作用最为明显;碱金属与碱土金属离子相比,碱金属条件下铜枝晶形状更为规则,观赏性更好;同时该反应速率与Cl^-浓度呈正相关。通过对反应条件的摸索,实现了将铝置换铜的所谓“铜树”反应改造为能在20 min内产生明显现象的课堂演示实验,可为金属置换反应和电化学腐蚀动力学教学创设情境,培育学生证据推理和模型认知的化学核心素养。     

跨学科融合实验：不锈钢皂的效果检验、原理探究与创新自制

不锈钢皂是用304不锈钢制作的肥皂,其有效性和原理存在争议。设计了跨学科融合实验,包括不锈钢皂的效果检验、原理探究与创新自制等3个主要环节。实验结果表明,不锈钢皂不能除菌,但能去除异味;其原理是物理吸附作用,而不是通过生成二价铁离子或三价铁离子与异味分子反应;可以通过物理打磨或化学腐蚀不锈钢表面、添加有效成分等多种方法自制不锈钢皂。实验基于生活情境中的真实问题,融合了化学、物理、生物、医学、通用技术等多学科知识和方法,培养学生解决跨学科问题的能力。     

蒽与马来酸酐Diels-Alder反应的量化计算研究——介绍一个计算化学实验

蒽与马来酸酐的Diels-Alder反应是基础有机化学实验课程中普遍开展的一个经典实验。本文推荐蒽与马来酸酐Diels-Alder反应的计算化学实验,该实验采用Gaussian 16程序中的密度泛函方法对蒽和马来酸酐Diels-Alder反应的反应机理进行了研究。旨在通过本实验激发学生对有机化学和计算化学的兴趣,加深学生对化学学科的理解,提升学生在科研工作中学以致用的能力。     

基于绿色化学的甲烷与氯气取代反应装置优化设计

针对传统甲烷与氯气取代反应实验装置存在环境不友好、实验装置较大、过于分散、反应难以定量化等缺陷,从绿色化学角度出发,对传统甲烷与氯气取代反应装置进行优化设计,实现了该实验过程的绿色化,实验装置的微型化、综合化和反应的可控化、定量化。     

智能手机色度分析测定甲基紫与氢氧化钠反应速率常数

化学反应速率是反应动力学最基本的一个概念,化学反应速率常数的测定是基础化学实验中的必做实验。但该实验存在着试剂消耗量大等诸多缺点。本次实践活动从绿色化学理念出发,提出了通过将色彩理论与化学知识结合进行反应速率的测定,以达到节省实验所用试剂、提高学生对实验的兴趣等目的。首先调研了解学生对经典动力学实验的看法和利用智能手机进行化学实验的接受度,并在理论上对该方法的可行性进行了分析,再根据录制的甲基紫与NaOH反应的视频,通过色度分析获得了浓度随时间变化的曲线,由此测定了该反应的反应速率常数。该方法结合了互补光色理论、物质吸光定律等知识,只需利用智能手机和取色软件就可以开展动力学实验。     

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.