原子的边界半径

本文建议和讨论2了原子大小的一种新量度-原子的边界半径, 经出了边界半径的周期表。对于惰性气体原子和汞原子, 有实验测得的有效半径, 它们与边界半径符合得相当好。原子的边界半径与实验的van der Waals半径有良好的线性关系。因此, 由边界半径可以预言某些原子的有效半径以及van der Waals半径。     

离子质电比和相差异因子对离子半径的的综合标度

依据已建立的离子质电比和相差异因子对离子半径的标度方法,系统性地研究了非稳定构型阳离子的相差异因子,采用回归分析法,改进了非稳定构型阳离子半径的计算公式。将稳定构型阳离子半径公式推广到等电子阳离子半径系统,计算了ⅡA(B)-ⅦA族52种离子半径数据;用改进的非稳定构型阳离子半径公式计算了四到七周期过渡元素(包括镧系和錒系),+1到+8各价态阳离子半径373个,其中预测了较为合理的271种阳离子半径数据。与前文中稳定构型阳离子半径合在一起,共108种元素508种离子半径,这些数据随周期数、族数以及价态等变化十分规律,是一套较好的、较为完整的单原子离子半径数据。     

离子半径的质量和电量综合因子的标度

根据作者曾建立的万有引力势与电势的关系式和系统的对比质电比(单位电量的质量)Sr的物理意义, 研究了离子半径r与Sr的关系: 对于相同电子构型的阳离子, 离子半径与lgSr呈线性关系; 对于相同电子构型的阴离子, 离子半径与Sr的关系满足Michealis-Menten 数学模型. 采用回归分析方法, 拟合出周期表中94种元素108种阳离子的半径和16种阴离子的半径. 从相关系数R和回归方程的显著性检验(F)都说明r与Sr密切相关, 其中102种阳离子半径数据与具有代表性的离子半径参考值相比平均绝对误差仅0.9 pm, 相对误差1.1%. 同时给出一条获取离子半径(包括复杂离子)数据的新途径.     

对某些教材叙述Goldschmidt离子半径的一点修正

现行的《物质结构》、《结晶化学》或《物理化学》教材在阐述离子半径时,除介绍Pauling的晶体半径和Shannon的有效半径以外,一般都介绍了Goldschmidt的离子半径.但某些教材在谈到用Goldschmidt方法推引MgO中Mg~(2+)离子的半径时有失严谨或欠完善.例如近年山东教育出版社出版的一本《结晶化学》,在叙述离子半径的测定时有这样一段话:“但是已知r_(o~(2-)),却不能从MgO求得r_(Mg~(2+)),因为在MgO中尚无法确定正、负离子的接触情况,只能推出r_(Mg~(2+))~2.10-1.40=0.70A”.这一段话是不恰当的.事实上,我们可以设法确定MgO中正、负离子的接触情况并求出r_(Mg~(2+)).为此,我建议将它改为:“已知r_(o~(2-))=     

金属材料分析方法的选择和施行第六讲金属材料中稀土元素的测定(续)

钇的离子半径介于镝与钬之间,因此它的性质更接近于重稀元素。当元素的价态发生变化时,离子半径也发生变化。例如三价铕离子的半径为1.13,而二价铕的半径就增加到1.2~1.3,这就与锶的离子半径(1.27)接近了。因此,二价铕离子的性质与碱土金属离子比较相似,因而,就有可能用硫酸锶来共沉淀铕,以富集微量的铕。表6-3中还列出了稀土元素三价离子的颜色,可作为鉴别的参考。1.4镧系元素的化学性质在1.2及1.3节中简要地提到了镧系元素的电子结构和价态的关系以及镧系收缩和原子半径,离子半径的递变规律。这些元素的上述性质和现象对它们的化学性质也…     

离子质电比和相差异因子对离子半径的综合标度

根据万有引力势与电势的关系式和系统的质电比(单位电量的质量)Sr的物理意义, 研究了离子半径r与离子的Sr和相差异因子的关系. 对于阳离子, r与lgSr和相差异因子呈线性关系; 对于稳定构型阴离子, r与Sr和相差异因子也存在定量关系. 采用回归分析方法, 给出稳定构型和非稳定构型阳离子半径计算公式, 以及稳定构型阴离子半径计算公式. 从相关系数R和回归方程的显著性检验(F)都可说明r与Sr和相差异因子密切相关, 其中拟合的96种元素的138种阳离子半径数据与具有代表性参考值相比, 平均绝对误差为2.0 pm, 相对误差为2.5%. 并预测出较为合理的稀有气体等30种离子半径数据. 同时给出一条获取离子半径(包括复杂离子)数据的新途径.     

环式结构体系中的双碳正离子

在某些环式结构体系中,由于某些轨道的相互作用使正电荷离域,从而克服正电荷间的相互排斥形成长寿命的双碳正离子。本文介绍苯双碳正离子,双环[m.n.p]桥头双碳正离子、去氢金刚烷基双碳正离子及宝塔烷双碳正离子的生成、检测、性能及理论处理。     

戈德施米特：地球化学和晶体化学的奠基人

戈德施米特(1888—1947),地球化学的奠基人,他发现了元素在地球中的分布规律。他在元素的相对丰度、原子和离子半径、离子间距、半径比对晶体配位数的影响、镧系收缩等方面的成果,为晶体化学奠定了基础。本文介绍了戈德施米特的生平和成就。     

戈尔德施密特:地球化学和晶体化学的奠基人

戈尔德施密特(1888—1947)是地球化学的奠基人,他发现了元素在地球中的分布规律。他在元素的相对丰度、原子和离子半径、离子间距、半径比对晶体配位数的影响、镧系收缩等方面的成果,为晶体化学奠定了基础。本文介绍了戈尔德施密特的生平和成就。     

碳正离子相对稳定性的定量判断

利用某些碳正离子稳定性的活性指标,将碳正离子相对稳定性的定性解释提高到定量表述的水平.尤其对某些碳正离子用电性效应难以解释清楚的问题,采用文中介绍的几种活性指标都能得到较正确的结果.     

Interactions of nucleobases with alkali earth metal cations--electrospray ionization mass spectrometric study

Interactions of nucleobases with alkali earth metal cations have been studied by electrospray ionization mass spectrometry (ESI-MS). Nucleobases containing at least one oxygen atom form stable complexes with alkali earth metal cations. This phenomenon can be explained on the grounds of the well known theory of hard and soft acids and bases. Uracil and thymine make complexes only when in their deprotonoted forms. The cations of great radii (Sr(2+), Ba(2+)) are more prone to form complexes of stoichiometry 1:1 with uracil and thymine than the cations of small radii (Mg(2+), Ca(2+)). On the other hand, Mg(2+) forms complexes of stoichiometry 2:1 and 3:2 with uracil and thymine. Gas-phase stabilities of the 1:1 complexes are higher for the cations of small radii, in contrast to the solution stabilities. For cytosine and 9- methylhypoxantine the 1:1 complexes of their deprotonated forms are observed at higher cone voltage as a result of HCl molecule loss from the complexes containing the counter ion (Cl(-)). In solution, more stable complexes are formed with metal cations of low radii. Gas-phase stability of the complexes formed by deprotonated 9- methyl-hypoxantine increases with increasing metal cation radius.     

阳离子替换磷灰石固溶体的比晶体化学

利用XTD,IR对不同阳离子替换的磷灰石(Ap)固溶体进行了比较晶体化学研究,结果表明：端元二价阳离子对Ap晶格常数(a0,c0)影响是线性的,符合Vegard规律,有较好的x-V习性,可作为阳离子半径测定的"结构尺";对于Cl-PO4体系的Ap,端元离子半径须在0.095～0.134nm之间才能形成空间群为P63/m的Ap结构;异价固溶体可以研究Ca(1)、Ca(2)位置的结晶化学差异,Ca(2)位在晶核形成期生成且决定了晶胞的框架,而Ca(1)位主要影响Co;随阳离子半径增加,[PO4]四面体的ν4,ν3,ν1红外振动峰向低频方向红移;Ap结构中发现"铅异常",形成原因是铅在Ca(2)位的较大电负性。     

Effect of cation on the performance of AC/graphite capacitor

The effect of cation on the performance of activated carbon (AC)/graphite capacitor has been studied. Electrolytes using Li⁺ and four kinds of quaternary alkyl ammonium cations have been picked up for this investigation. The relationship between the ionic radii of cations and the specific capacitance of AC negative electrode in corresponding electrolytes has been correlated. The state of Li⁺ dissolved in PC (propylene carbonate) solvent has also been clarified.     

Nickel ferrocyanide modified electrodes as active cation-exchange matrices: real time XRD evaluation of overlayer structure and electrochemical behavior

The dynamic variations in the structure of nickel ferrocyanide modified electrodes was determined using in situ diffractoelectrochemical techniques. X-ray powder diffraction peaks from the nickel ferrocyanide modified electrode were recorded during electrochemical oxidation/reduction of the surface overlayer and reversible changes in the unit cell lattice parameter observed. The electrochemical changes that occur during oxidation/reduction in various alkali cation electrolytes are correlated with changes in the lattice parameter. It is postulated that micro-domains form when two cations having markedly different radii such as cesium and potassium are intercalated into the nickel ferrocyanide structure so that distinct regions of the nickel ferrocyanide layer containing cesium exist separated from regions with the lighter alkali cations.     

Conductance of 1:1 cobalt(III) amine complex salts in liquid ammonia

Electrical conductance behavior of a number of symmetrical, univalent tetraamine- and bisethylenediamine cobalt (III) complex salts in liquid ammonia was investigated. Ion-pair association constants were obtained by applying the conductance equations of either Pitts, Fuoss or Lee and Wheaton. The association constants found are remarkably independent of the nature of the inner-sphere ligands, but are sensitive to the geometrical configuration (cis/trans) of the cobalt (III) cation and the radius of the anion. Walden products and Stokes' radii of the cations are presented and discussed.     

Specific alkali cation effects in the transition from micelles to vesicles through salt addition

The transition of ionic micelles to vesicles with added salts is explored in this paper. The catanionic surfactant solution was comprised of sodium dodecylsulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) with an excess of SDS. The micellar size increased with concentration for all salts. No anion specificity was found, probably because of the excess of SDS. However, when the cation of the added salt was varied, large differences were observed in the hydrodynamic radii of the aggregates. A classification of the cations according to their ability to increase the measured hydrodynamic radii follows a Hofmeister series. The change in aggregate size can be explained by modified counterion binding and dehydration of the surfactant headgroups.     

Features of adsorption phenomena in strontium salt solutions in the presence of some cavitands of cucurbituril family

The influence of the electrolyte nature and cation charge on the adsorption properties of cucurbit[6]uril supramolecular complexes are established and discussed. The results show the narrowing of the adsorption potential region of these complexes with increasing cation charge, and the possibility to form an adsorbate layer of supramolecular cations associated with surface-active electrolyte anions at the positive boundary of the adsorption potential region.     

Visible light-induced charge storage, on-demand release and self-photorechargeability of WO3 film

Tungsten oxide (WO(3)) electrodes subjected to a positive bias are self-photorecharged with alkali cations in the electrolyte during visible light illumination. Upon photoexcitation, part of the photogenerated charges generated by WO(3) is stabilized by the cations and stored in situ within the WO(3) framework. This light-induced storage of charges is subsequently utilized in dark conditions in an on-demand manner and is able to be recharged in the successive illumination cycles. The amount of charges stored is shown to be dependent on the cation ionic radii and the presence of these intercalated cations is verified by X-ray diffraction (XRD) and inductively coupled plasma mass spectroscopy (ICP-MS). This self-photorecharge and on-demand charge-release phenomena demonstrate the ability of WO(3) to supply photoexcited charges under dark condition in a photoelectrochemical reaction with greater flexibility.     

Salt effects on the phase behavior, structure, and rheology of chromonic liquid crystals

Chromonic liquid crystals are formed by the addition of aromatic molecules such as disodium chromoglycate (cromolyn) to water. In this study, we investigate the addition of salts to the lyotropic nematic phase of cromolyn aqueous solutions. The addition of sodium and potassium salts shifts the isotropic-nematic phase boundary upward by more than 10 degrees C, so that samples that were isotropic at room temperature are transformed into nematic phases. Salt effects are predominantly dictated by the cation, not the anion, and appear to differ based on cation size. In contrast to small, hydrated cations like sodium, large, weakly hydrated cations such as tetraethylammonium and tetrabutylammonium shift the phase boundary downward, thus stabilizing the isotropic phase at the expense of the nematic one. The phase behavior results are highly correlated with viscosity measurements, with an upward shift in the phase boundary correlating with an increase in solution viscosity and vice versa. We also probe the microstructure in cromolyn-salt solutions, both indirectly by small-angle neutron scattering (SANS) and directly by cryo-transmission electron microscopy (cryo-TEM). The cryo-TEM images show the presence of rodlike aggregates that possibly undergo a higher order aggregation into bundles in the presence of salt.