略论现代酸碱理论的发展

本文简要地叙述了酸碱理论的发展过程,其中主要介绍了现代五大酸碱理论。即水-离子论、溶剂论、质子论、电子论和硬软酸碱概念,较详细地阐述和分析了它们各自的优点和局限性。     

软硬酸碱理论的发展和应用

从软硬酸碱理论的起源出发,简要介绍软硬酸碱理论的建立背景、发展过程,并对其可能的应用范围做了讨论.最后结合人们对于软硬酸碱理论的认识和应用现状,做出总结和评价.     

教材做加法学业做减法——以酸碱质子理论视角下盐类水解的教学设计为例

以酸碱电离理论和酸碱质子理论视角下盐类水解的教学设计为基础,阐述选取高中知识自然增长点作为教学资源帮助学生形成系统化学观,培养学生的深层理解能力和科学思维能力,从而达到教材做加法,学业做减法的可能性。     

从“最强酸碱”话题入手介绍超强酸、超强碱

酸碱质子理论是普通化学中的重要模块。学习酸碱质子理论一般从弱酸水溶液入手,若将应用范围扩展为所有含质子的化合物,该理论将被赋予更多的内涵。在含质子的已知化合物中,K_a的范围十分宽广,跨越了100个数量级以上。哪种酸碱“最强”一直是学生间喜闻乐见的话题,以此话题出发,介绍了常见的超强酸、超强碱与相关概念及应用。这些概念的介绍不仅拓展了学生的视野,更能够加深学生对酸碱质子理论的理解,对未来分析化学、无机化学、有机化学的教育产生积极意义。     

酸碱软硬度的理论研究

Pearson 从大量的实验事实归纳出的软硬酸碱原理广泛地应用于解释许多化学现象,还应用于评价和预料化学反应,极为简便、实用。然而,软硬酸碱原理的理论基础尚在不断地充实之中。近来微扰理论和密度泛函理论研究的结果表明:软硬酸碱能成功地描述化学反应,有明确的物理意义。现在(?)将定域硬度(或软度)和分子的化学活性定量地联系了起来。本文指出了酸碱软硬度键参数与物质性质定量研究的美好前景。     

质子酸的酸性强弱比较

酸碱质子理论是大学无机化学教学中最重要的概念之一,溶液中的酸碱强弱的比较虽然可以通过查找酸碱解离常数来得到,但在数据缺失情况下的定性比较酸碱强弱在教学中也很重要,而且这种比较可以帮助学生理解物质结构与性质之间的相关性。本文根据质子酸碱的化学组成和分子结构分析它们的酸碱性,并主要根据分子结构信息,包括键的极性、键的强度、键的离域、氢键、分子中键的环境等,推导、比较它们酸碱性的相对强弱。     

酸碱指示剂的发展方向

介绍了酸碱指示剂的基础知识和选择依据,重点介绍了目前天然植物色素在酸碱指示剂和酸碱滴定中的应用。同时,由于新技术的快速发展,基于纳米技术和DNA结构转变的无污染环保指示剂更加值得关注。     

基于多元外在表征理论的酸碱中和滴定概念教学设计

在多元外在表征教学理论的基础上,提出了酸碱中和滴定的教学设计,主要包括创设酸碱中和滴定实验情境、引入酸碱中和滴定概念与原理、介绍滴定管、选择指示剂、演示实验、使用Netlogo解释酸碱中和滴定等内容。研究结果表明该教学设计能帮助高职生更好地理解“酸碱中和滴定”知识。     

谈非水酸碱滴定的理论体系

以酸碱质子理论为基础，把分散在水和非水酸碱滴定各章节中的有关常数和公式系统地连贯起来，阐明了它们的关系和意义。     

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。     

Solid Acid-Base Control of Inorganic/Organic Hybrids by Inorganic Components for Molecule-Selectivity

Solid acid-base properties of methylsiloxane-based inorganic/organic hybrids were controlled by incorporation of inorganic components other than Si into methylsiloxane networks. The effect of different inorganic components on the solid acid-base properties was estimated by first-principles calculations based on density functional theory (DFT). The deprotonation tends to occur in the order Si < Al < Nb inorganic components, suggesting that the acidity increases in the same order. Methylsiloxane-based hybrids with solid acid-base properties were also synthesized by incorporating inorganic components derived from metal alkoxides. Hammett indicators revealed that the solid acidity increased in the order Si < Al < Nb inorganic components, which was consistent with the results of first-principles calculations. Preliminary experiments revealed that the methylsiloxane-based hybrids also provided a solid basic nature by containing Ca and Y inorganic components derived from metal alkoxides. The acidic hybrids were found to have Brønsted acid sites from the FT-IR experiments of adsorbed pyridine on the hybrids.     

Acid-base properties of alumina prepared from a hydrated product of centrifugal thermal activation of hydrargillite (cta-product)

Summary Acid-base properties of aluminas prepared by thermal treatment of a hydrated CTA-product at 600°C were studied. The CTA-oxides, representing γ-Al₂O₃, were shown to contain terminal and bridged OH-groups. The concentration of the terminal OH-groups in the CTA-oxides was found to exceed their concentration in γ-Al₂O₃ prepared by dehydration of the “precipitated” pseudoboehmite, whereas the concentration of the bridged OH-groups in the CTA-oxides was lower than that in γ-Al₂O₃ prepared from pseudoboehmite. The total concentration of the surface Lewis acid sites in CTA-oxides varies within the limits of 2.80-4.14 mmol/m² and is essentially above that in g-Al₂O₃ (2.25 mmol/m²). The distinctive feature of the CTA-oxides is that their surface contains strong Lewis acid sites with n_CO = 2220 and 2238 cm^-1. The total concentration of basic sites in the CTA-oxides is lower than that in g-Al₂O₃, however, in contrast to g-Al₂O₃,they contain strong basic sites with n_CDCl3 = 2200 cm^-1.     

Structure and acid-base properties of hexaaluminates

Hexaaluminates SrAl₁₂O₁₉, BaAl₁₂O₁₉ and LaAl₁₁O₁₈ were prepared by co-precipitation of soluble nitrates of Sr, Ba, or La and Al using NH₄HCO₃ as a precipitating agent with subsequent calcination at 700–1400°C. The samples were characterized by adsorption methods, thermal analysis (TA and DTG), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy of adsorbed probe molecules (CO and CDCl₃). It was shown that calcination at 1200°C resulted in the formation of single-phase hexaaluminates in all the samples except for LaAl₁₁O₁₈, where an additional phase was found. The specific surface area of the samples was obtained in the range 16–22 m²/g. After the treatment at comparable conditions, the total concentrations of both surface Lewis acid sites and basic sites were found to increase in the series: BaAl₁₂O₁₉ < SrAl₁₂O₁₉ < LaAl₁₁O₁₈. However, the strongest basic sites were detected on the surface of BaAl₁₂O₁₉.     

聚酰胺-胺的酸碱电位滴定分析

聚酰胺-胺(PAMAM)是一种有着广泛用途的树形大分子,酸碱滴定分析可以表征合成的PAMAM中所含的伯胺基及叔胺基的数量,因此作为一种重要的辅助表征手段被PAMAM的合成及改性研究者所采用。文章对该方法原理进行了详细的论述,说明了滴定过程中产生的酰胺键水解不影响滴定及计算结果。通过实验表明在pH<2的条件下滴定可以保证叔胺的充分质子化。     

Titanium(IV) phosphinoamide as a unique bidentate ligand for late transition metals II: TiRu heterobimetallics bearing a bridging chlorine atom

Treatment of a titanium phosphinoamide, (Ph₂PN^tBu)₂TiCl₂ (1), with [Cp^∗RuCl]₄ in THF at room temperature afforded a TiRu heterobimetallic complex, of which crystallographic study showed the molecular structure to be a six-membered dimetallacyclohexane, Cp^∗Ru(μ-Cl)(Ph₂PN^tBu)₂TiO (3). A boat conformation of the dimetallacycle leads to effective linking of the two metal centers by two phosphinoamide ligands, and bridging of a chlorine atom over the TiRu axis. The TiRu heterobimetallics were synthesized by the reaction of 1 with Cp^∗Ru(COD)Cl or Cp^∗Ru(TMEDA)Cl, whereas no reaction occurred between 1 and Cp^∗Ru(PCy₃)Cl. A primary product of this reaction would be a trichloride, Cp^∗Ru(μ-Cl)(Ph₂PN^tBu)₂TiCl₂ (2). In fact, careful treatment of 1 with [Cp^∗RuCl]₄ afforded 2 as the main product which was detected by NMR and ESI-MS spectra; 2 was converted to 3 in contact with 1 equivalent of water.     

优势区域图在分析化学教学中的应用

在酸碱平衡及络合平衡中,利用分布分数可以定量地说明不同条件下溶液中各种组分的分布情况,据此可以绘制优势区域图。利用优势区域图不仅能够简单、直观、方便地分析优势分布的情况,还可用于处理许多关于平衡和滴定的问题。结合具体的实例对于优势区域图的绘制及在分析化学教学中的应用进行了论述。     

Structural characterization of a completely alkyl-substituted Al-Sb Lewis acid-base adduct

The Lewis acid-base adduct t-Bu₃Al-SbMe₃ (1), which was synthesized by reaction of equimolar amounts of t-Bu₃Al and trimethylstibine SbMe₃, was characterized by multinuclear NMR (¹H, ¹³C) spectroscopy, elemental analyses as well as by single crystal X-ray diffraction.     

酸碱型体分布系数计算的新方法

基于代数法,借助浓度对数图建立了一种计算酸碱型体分布系数的新方法。用该方法计算酸碱型分布系数,仅需对ＰＨ值及相关ＰＫａ值作加减衣简单的对数和指数运算,计算结果与代数法吻合。     

Oxidative dehydrogenation of ethane over movmnw oxide catalysts

Catalysts based on mixed oxide of MoVMn are active at relatively low temperature for oxidative dehydrogenation of ethane. Incorporation of tungsten into MoVMn oxides enhances the catalytic activity. Enhancement of the activity is explained in the light of acid-base interaction accompanied with a redox mechanism of surface reoxidation. This revised version was published online in June 2006 with corrections to the Cover Date.