希托夫法求离子迁移数计算通式

在研究电解质溶液理论时,通过计算离子迁移数,可以求出电解质溶液中离子电导、离子淌度、电位梯度等一系列重要物理量。离子迁移数常用的实验室测定方法有:希托夫(Hittof)法、界面移动法和电动势法。其中希托夫法在目前物理化学教材中没有简便统一的计算公式可循。笔者结合教学实践,根据离子迁移数定义与不同情况下离子在阴、阳极区电解前后浓度变     

电动势法测定硫酸铜的离子迁移数

离子迁移数作为物理化学的重要参数,其测定是大学物理化学实验中的基础内容.以基础物理化学实验中离子迁移数的测定为基础,结合电动势的测定等实验,设计建立了一套电动势法测量溶液中铜离子与硫酸根离子迁移数的实验装置,得到的离子迁移数与文献值基本一致.尝试基于大学生在物理化学实验中已掌握的实验技能,综合电化学学科领域的知识,设计探索电动势测量离子迁移数的新方法,有助于提升学生对知识的综合运用能力.     

希托夫法中离子迁移数的计算

本文提出了一种用于希托夫法中求算离子迁移数的新方法。与常规方法相比，它具有简单明了、易于掌握的特点。     

离子迁移数测定中各物质的量的关系

离子迁移数测定中各物质的量的关系张光玺（云南大学化学系昆明６５００９１）在物理化学教材中，离子迁移数测定方法之一是希托夫（Ｈｉｔｔｏｒｆ）法。其基本原理是：通电于电解质溶液之后，溶液中的正、负离子分别向阴－阳两极移动，并在相应的两极界面上发生还原或氧...     

等价无穷小与合比定律在物理化学教学中的应用

利用等价无穷小的理论结合物理化学中环境熵变、理想稀溶液溶剂化学势和高聚物的相关概念分析了环境熵变、理想稀溶液溶剂化学势的计算公式和"黏度法测定高聚物相对分子质量"实验中的关键理论推导。利用合比定律与物理化学的杠杆规则、离子迁移数等知识点推导出杠杆定律和离子迁移数的相关公式。使抽象的、不易掌握的物理化学知识具体化,便于学生理解、掌握和运用。     

迁移管形状对希托夫法测定离子迁移数结果的影响

在希托夫法测定Cu~(2+)离子迁移数的物理化学实验教学中,目前常用直形和U形两种类型的迁移管,其中使用U形迁移管从阴极区溶液浓度变化算出的迁移数误差较大。以CuSO_4为电解质,Cu电极为电解电极,采用分光光度法分别测定了通电后直形、U形和n形三种迁移管中CuSO_4溶液浓度随高度的分布情况。研究发现,迁移管的形状对中部区溶液的浓度有较大影响。对于U形和n形迁移管,由于阴极位于迁移管底部,主要受重力作用引起的对流因素的影响,通电后中部区浓度会发生明显改变,并影响到阴极区溶液浓度,导致误差较大;使用直形迁移管受该因素的影响很小,能得到更为准确的结果。     

综合理化知识解析离子迁移数和淌度的测定实验*

基于大学物理化学基础电化学实验--界面移动法测定离子迁移数和离子淌度,讨论了(1)氢离子迁移数的表达;(2)镉离子和氯离子的离子迁移数;(3)恒电流条件下离子的匀速直线运动;(4)氢离子和镉离子电位梯度的求解;(5)摩尔电导率与离子淌度的线性关系;(6)实验条件下的电化学反应等内容。做了3组平行测定实验,并结合实验数据对前述内容特别是前4项内容进行了讨论和分析。讨论整合了化学和物理学等多个学科的知识,有助于学生优化知识体系,进而提高其化学学科核心素养。     

希托夫法测定离子迁移数实验的教学改革研究

希托夫法是物理化学实验中测定离子迁移数的传统方法。在教学实践中发现,传统实验装置及操作方法易因待测溶液对流、扩散或人为操作失误等问题导致测定的离子迁移数不准确,因此有必要改进该实验的装置和操作方法。本文提出通过调整测量装置中U型迁移管的玻璃活塞数量,改进装液、溶液收集、滴定操作等实验步骤,降低实验操作难度,增加同批样品的滴定分析次数,提高实验结果的准确性。同时减少近70%的废液产生量,降低了教学成本,减少了环境污染。本研究能够激发学生的实验研究创新意识,促其建立污染物减排的环保观念。     

应用模式耦合理论求离子极限摩尔电导率

在模式耦合理论推导的低浓度时离子摩尔电导率与离子浓度的关系式中,引入离子迁移数,提出了求离子极限摩尔电导率的新方法。应用该方法计算了7种锂盐在2种单一有机溶剂和2种混合有机溶剂中正、负离子的极限摩尔电导率。计算结果与文献中采用经验公式计算迁移数得出的结果和文献中根据电化学电池法测定迁移数得出的结果相符。     

界面上的特异离子效应

结合物理化学教科书的相关章节,介绍卤化钠在固/液和气/液界面中的特异离子效应,提出在物理化学基础教学过程中应适当地结合相关领域的最新进展,拓宽学生的知识视野,更好地激发学生的学习兴趣。     

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%.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.