某些氢酸的pK_α值的经验计算法

对于周期系中第Ⅴ、Ⅵ、Ⅶ类主族元素所形成的某些氢化物的酸碱性及其酸碱强度的经验计算法,前人虽然有过不少论述,但还没有一个统一的计算式。本文试图从这些元素的两个基本性质,原子共价半径和价电子数出发,对它们的氢化物在水溶液中的酸碱性强弱,提出一种较为简便的经验计算法。一个化合物在溶液中的电离,既决定于它本身的内部结构,又决定于溶剂的性质,当我们讨论这些氢化物在水溶液中酸碱性强弱的规律时,因为介质相同,它们的酸碱性强弱主要决定于其分子结构。对 H_aX 型氢化物而言(a 为氢原子数,a=8-n,n 为 X 原子的     

广义酸碱体系电极电势的设计和应用

根据路易斯酸碱理论,把任何广义的酸碱反应,设计出一定形式的可逆电池,计算电池电动势,可以判断酸碱加合反应的方向,生成的加合物的稳定性,以及广义酸碱的酸碱性强弱等性质。     

酸碱强弱的規律及經驗計算法

在高等学校无机化学教学过程中,对于酸和碱,同学们经常发生这样或那样的问題,本文将试用酸碱的质子理论,来说明酸碱强弱的规律和一些经验计算法。     

共价型氢化物的酸碱性

周期系第4—7主族元素和第3主族的硼与氢化合均生成共价型氢化物,又称挥发性氢化物(不讨论碳的各种碳氢化物)。它们中约半数在水中溶解呈现酸性或碱性。对其酸碱性及强度等规律的解释前人有过不少理论,但均不够满意,往往不能全面解释,也不能解释自身电离问题。本文试从分子结构出发以有效电荷及溶剂影响等方面结合起来说明其规律性。一、从分子中电子化合状态看酸碱性化合物是酸还是碱,即能给出质子还是能接受质子决定于其分子结构。分子中的原子有在合适的条件下尽量利用其价电子的倾向。如果其价电子还没有完全利用,分子就会显示一定的活泼性。例如含有未共     

脂肪胺、醇HOMO能级与质子亲和能关系

20世纪 70年代前后 ,随着离子回旋共振 (ＩＣＲ)实验技术的发展 ,在气相条件下能够进行有机化合物质子亲和能的测定 ,摆脱了复杂溶剂化作用的干扰 ,可以直接研究分子结构与有机化合物气相酸碱性的关系 ,加深了人们对取代基效应的认识 ,为进一步研究溶剂化效应对有机化合物性能的影响奠定了基础 .因此 ,分子结构与气相酸碱性的关系研究成为人们感兴趣的课题之一 .迄今 ,在探讨有机同系物气相碱相与分子结构关系问题的研究方面 ,大体分为两类 :一类是采用经验或半经验参数 (如取代基电子效应参数 )与质子亲和能相关联[1,2 ] ;另一类是利用量子…     

酸碱支配区图在化学教学中的应用

在化学教学中半定量地使用酸碱支配区图,在今天仍然有一定的现实意义。用酸碱支配区图可以直观地展示出在水溶液中弱酸和弱碱离子间的质子传递过程是如何进行的。用酸碱支配区图能确定一些弱酸弱碱盐水解的程度和形式,能判定一些多元酸碱相互反应的产物及反应方程式,能描述出一些有自身质子传递反应的化学反应过程。     

零水准法在酸碱滴定体系中的实际应用——介绍终点误差公式推导的一种简便方法

酸碱质子理论奠定了酸碱平衡和酸碱滴定体系定量处理的理论基础,这已为分析化学界所公认。处理问题的关键在于首先如何准确地导出平衡体系中的质子等衡式即质子条件(简写pBE)。质子条件可以根据溶液的物料平衡和电荷平衡关系导出,也可以由溶液中得失质子关系即零水准法直接写出。前者涉及到某些不参与质子转移物质之间的平衡关系,处理繁琐,易出差错。后者处理问题具     

关于酸碱滴定教学中的一些问题

酸碱滴定是基础分析化学中最重要的内容之一。通过酸碱滴定的教学,不仅有利于学生掌握滴定分析法的基本原理,而且为比较严谨地处理分析化学中各种化学平衡问题打下牢固的基础。因此,新编分析化学教材对酸碱滴定一章有所加强,与过去的教材相比,内容的改变也较大,而变化最大的是用酸碱质子理论来定量处理酸碱平衡问题。其他如溶液中各种酸碱组分的分布、溶液pH值的精确计算、缓冲容量、终点误差和非水滴定等内容,也有所加强。本文拟对用质子理论处理酸碱平衡和终点误差     

镁与铵盐溶液反应的教学分析

根据酸碱质子理论,NH4+是一种可提供质子的酸。铵盐溶液在与Mg反应中,根据具体的实验事实可以证明氧化剂不是H2O,而应是NH4+氧化了Mg,NH4+自身被还原为H2和NH3。     

阳离子和氢氧化物在水溶液中的酸碱性

对于阳离子和氢氧化物(包括含氧酸)在水溶液中的酸碱性强弱的研究,无论在理论上还是在实用上都具有重要的意义,因为酸碱性是无机化合物最基本的性质之一。因此,进一步研究这类问题是很有必要的。一、阳离子在水溶液中的酸性按照Lewis酸碱理论,游离的阳离子都是酸,当它进入水溶液时,水分子与之配位,所形成的水合阳离     

The shape of the potential energy curves for NHN(+) hydrogen bonds and the influence of non-linearity

The potential energy curves for proton motion in NHN(+) hydrogen bonds have been calculated to investigate whether different methods of evaluation give different results: for linear H bonds most curves calculated along the NH direction are, as expected, identical with those along NN; for intramolecular H bonds it is very important to take into account the non-linearity and the potential energy curve calculated along the NH direction can be very far from the curve correctly describing the proton transfer. Other factors which influence the proton-transfer process are steric hindrance and presence of anions which modify the proton motion. In the analysis of the proton transfer process it is very important to take changes in the structure of the rest of the molecule into account, which is connected with exchange of energy with the surroundings. Comparison of adiabatic and non-adiabatic curves shows that they are significantly different for very bent hydrogen bonds and for hydrogen bonds with steric constraints for which the proton transfer process must be accompanied with relaxation of the whole molecule. Comparison of the potential-energy curves for compounds with very short H bonds emphasizes that the term 'strong H bond' needs to be qualified. For intermolecular H bonds shortening of the bond is connected with linearization. But for intramolecular H bonds the NN distance cannot be used as the only measure of H bond strength.     

The influence of short strong hydrogen bonding on the structure and the physicochemical properties of alkyl-N-iminodiacetic acids in solid state and aqueous systems

Alkyl-N-iminodiacetic acids with varying alkyl chain lengths have been prepared and characterized with respect to structure, acidic properties, and ability to form aggregates in water. The alkyl-N-iminodiacetic acids are the group of ligands with the lowest molecule weight which can be characterized as chelating surfactants, compounds with surface chemical properties which at the same time have a high ability to bind metal ions. The solid alkyl-N-iminodiacetic acids have a unique structure with neutral zwitterionic units linked together to polymer chains through a short strong hydrogen bond, d(O(-H)...O) approximately 2.46 A, and where the nu(O-H) stretching vibration at ca. 720 cm(-1) supports the presence of such a hydrogen bond. The polymer chains are cross-linked together to bilayers through relatively strong hydrogen bonds between ammonium and carboxylate groups, and where the parallel alkyl groups are interdigitating each other; the bilayer surface consists of hydrophilic iminodiacetic acid groups. The acidic properties of monomeric alkyl-N-iminodiacetic acids in water are in the expected ranges with pK(a) values of about 1.7, 2.3, and 10.3. n-Octadecyl-N-iminodiacetic acid, present as aggregates in water, displays very acidic properties of the first proton, and a substantially weakened acidity of the second proton, pK(a2) = 5.5-7.5, depending on ionic strength, and pK(a3) = 9.5-10.5. This pattern of the acidic constants strongly indicates that the polymer structure with short strong hydrogen bonds is maintained in the aggregates and that such bonds can exist in aqueous systems if they are supported by a strong and rigid backbone structure, as the bilayers of well-organized long interdigitating alkyl chains in the studied systems. Hydrogenbis(methyl-N-iminodiacetic acid) perchlorate precipitates from perchloric acidic solutions of methyl-N-iminodiacetic acid. The structure is built up of dimers of zwitterionic methyl-N-iminodiacetic acid units linked together by an extra proton in a short strong hydrogen bond, d(O(-H)...O) approximately 2.456(6) A, and nu(O-H) = 789 cm(-1).     

The crystallographic structure of a Lewis acid-assisted chiral Brønsted acid as an enantioselective protonation reagent for silyl enol ethers

It is difficult to control the enantioselectivity in the protonation of silyl enol ethers with simple chiral Br?nsted acids, mainly due to bond flexibility between the proton and its chiral counterion, the orientational flexibility of the proton, and the fact that the proton sources available are limited to acidic compounds such as chiral carboxylic acids. To overcome these difficulties, we have developed a Lewis acid-assisted chiral Br?nsted acid (LBA) system. The coordination of Lewis acids with Br?nsted acids restricts the orientation of protons and increases their acidity. Optically active binaphthol (BINOL) derivative.SnCl4 complexes are very effective as enantioselective protonation reagents for silyl enol ethers. However, their exact structures have not yet been determined. We describe here optically active 1,2-diarylethane-1,2-diol derivative.SnCl4 as a new type of LBA for the enantioselective protonation as well as its crystallographic structure. A variety of optically active 1,2-diarylethane-1,2-diols could be readily prepared by asymmetric syn-dihydroxylation. This is a great advantage over BINOL for the flexible design of a new LBA. The most significant finding is that we were able to specify the conformational direction of the H-O bond of LBA, which has some asymmetric inductivity, by X-ray diffraction analysis. The stereochemical course in the enantioselective protonation of silyl enol ethers using LBA would be controlled by a linear OH/pi interaction with an initial step. The absolute stereopreference in enantioselective reactions using BINOL.SnCl4 can also be explained in terms of this uniformly mechanistic interpretation.     

Influence of substitution, hybridization, and solvent on the properties of C-HO single-electron hydrogen bond in CH3-H2O complex

The effect of substitution, hybridization, and solvent on the properties of the C...HO single-electron hydrogen bond has been investigated with quantum chemical calculations. Methyl radical, ethyl radical, and vinyl radical are used as the proton acceptors and are paired with water, methanol, HOCl, and vinyl alcohol. Halogenation (Cl) of the proton donor strengthens this type of hydrogen bond. The methyl group in the proton donor and proton acceptor plays a different role in the formation of the C...HO single-electron hydrogen bond. The former is electron-withdrawing, and the latter is electron-donating, both making a constructive contribution to the enhancement of the interaction. The contribution of the methyl group in the proton acceptor is larger than that in the proton donor. The increase of acidity of the proton is helpful to form a single-electron hydrogen bond. As the proton acceptor varies from the methyl radical to the vinyl radical, the interaction strength also increases. The solvent has an enhancing influence on the strength of the C...HO single-electron hydrogen bond. These factors affect the C...HO single-electron hydrogen bond in a similar way that they do other types of hydrogen bonds.     

Regulating function of methyl group on the strength of dihydrogen bond in HBeH-HCCH and HMgH-HCCH complexes

The regulating function of methyl group on the strength of dihydrogen bond was investigated in HBeH-HCCH and HMgH-HCCH complexes at the MP2/6-311++G(3df,2p) level. The bond lengths, infrared spectra, interaction energies, and charge transfers were analyzed. The presence of methyl group in the proton acceptor enhances the strength of dihydrogen bond, whereas its presence in the proton donor weakens the strength of dihydrogen bond. The charge analyses indicate that the methyl group in the proton donor and acceptor is electron-donating, thus the methyl group in the proton donor plays a negative role, whereas in the proton acceptor it plays a positive role in the formation of dihydrogen bond.     

碱金属萃取化学的研究 III:弱酸性偶氮螯合剂化学结构对萃取锂的性能研究

The synergistic extractic extraction of lithium with a solution of o-phenylazophenols (HAX) and trioctylphosphine oxide (TOPO) or other trialkylphosphine oxide (TRPO, R = C8-10) in o-dichlorobenzene from aqueous solution of lithium hydroxide was reported. The structural effect of o-phenylazophenols on extraction of lithium has been examined. In the case of 1-(p-X-phenylazo)-2-naphthols, the HMO calculation shows that the charge density of azo nitrogen atom(the donor atom, denote azo N) and hydroxyl oxygen atom does not very apparently, so that the stability of their chelates with lithium has no obvious variations as well. In this case their ability to extract lithium is chiefly governed by the pKa. of the compound. The results of extraction prove that there is a linear correlation between the extraction constant Kex and pKa. However, for the second group of chelating agents, the change of their structure leads to the change of the change of both pKa and stability of chelates. The results of extraction and HMO calculation show that the stability of chelates is mainly influenced by the strength of the coordination bond, i.e. the larger the charge density of azo N (qN), the more stable the chelate will be. Therefore, their ability to extract lithium is roughly directly proportional to the stability of chelates and inversely to the pKa. the strength of coordination bond for the chelates can be experimentally measured by means of the strength of intramolecular hydrogen bond of chelating agent, ΔδOH (the diference of chemical shift of hydroxyl proton in free and bonded state). Therefore, the ratio, ΔδOH/pKa, can be used to evaluate the extraction ability of chelating agents to lithium. We find that it is approximately proportional to the distribution ratio (D).     

Relationship between 1H chemical shifts of deuterated pyridinium ions and Brønsted acid strength of solid acids

Deuterated pyridine (pyridine-d5) is one of the NMR probe molecules widely used for determination of acid strength of solid catalysts. However, the correlation between the 1H chemical shift of adsorbed pyridine-d5 and the Br?nsted acid strength of solid acids has rarely been investigated. Here, an 8T zeolite model with different Si-H bond lengths is used to represent the Br?nsted acid sites with different strengths (from weak, strong, to superacid) and to predict the pyridine adsorption structure as well as the 1H chemical shift. The theoretical calculation suggests that a smaller 1H chemical shift of the pyridinium ions on the solid acids indicates a stronger acid strength. On the basis of the results of theoretical calculations, a linear correlation between the pyridine-d5 1H chemical shift and the proton affinity (PA) of the Br?nsted acid site has been derived. In combination with the available 1H MAS NMR experimental data, we conclude that pyridine-d5 can be used as a scale to characterize the solid acid strength.     

A theoretical study of the hydrogen bond donor capability and co-operative effects in the hydrogen bond complexes of the diaza-aromatic betacarbolines

In this work, we present a quantum mechanical investigation on the hydrogen bond interactions of N(9)-methyl-9H-pyrido[3,4-b]indole, MBC, and N(2)-methyl-9H-pyrido[3,4-b]indole, BCA, with different hydrogen bond donors. Thus, it has been analysed the influence that the hydrogen bond donor strength and the co-operative effect of the increasing number of donor molecules have on the shape of the potential energy surfaces versus the N···H distances, r(N–H). To rationalize the nature of the interactions, the Bader theory has been applied and the characteristics of the bond critical points analysed. The results show that two different hydrogen bond complexes can be formed depending on the donor capabilities or the number of donor molecules included in the calculations. The topological parameters from the Bader theory are used to justify the statement that the analysed interactions can be classified as weak or partially covalent hydrogen bond interactions, respectively. As experimentally observed, weak hydrogen bond donors form weak hydrogen bond complexes, called HBC. Upon the increase of the donor strength the N···H proton is shifted nearest to the nitrogen atom giving rise to the observation of a stronger hydrogen bond complex, the proton transfer complex, PTC. The most outstanding result of these studies is the fact that the formation of the PTC can also be managed just by changing the number of donor molecules, that is, by a co-operative effect of the hydrogen bonds.     

Theoretical study of CH…O hydrogen bond in proton transfer reaction of glycine

Density functional theory (DFT) calculations are used to study the strength of the CH…O H‐bond in the proton transfer reaction of glycine. Comparison has been made between four proton transfer reactions (ZW1, ZW2, ZW3, SCRFZW) in glycine. The structural parameters of the zwitterionic, transition, and neutral states of glycine are strongly perturbed when the proton transfer takes place. It has been found that the interaction of water molecule at the side chain of glycine is high in the transition state, whereas it is low in the zwitterionic and neutral states. This strongest multiple hydrogen bond interaction in the transition state reduces the barrier for the proton transfer reaction. The natural bond orbital analysis have also been carried out for the ZW2 reaction path, it has been concluded that the amount of charge transfer between the neighboring atoms will decide the strength of H‐bond. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Kinetics and equilibria of proton exchange in the lowest excited singlet states of 8-methoxyquinoline and 8-methoxyquinaldine: analysis of some complex fluorimetric titration curves

The determination of the rate constants for proton exchange in the lowest excited singlet states of 8-methoxyquinoline and 8-methoxyquinaldine from the pH dependences of their fluorescence spectra is complicated by overlap of the spectra of the conjugate acids and bases of both compounds and by the enhancement of 8-methoxyquinoline fluorescence at high pH by a process apparently unrelated to proton exchange. The fluorimetric titration data are analyzed in ways which compensate for these difficulties and the kinetic parameters of excited-state proton exchange determined. Qualitative relationships between the parameters of excited-state proton exchange, electronic structure and steric factors are considered.