氩元素概念的形成和发展与化学思想的演进

19世纪末英国化学家瑞利和拉姆塞发现了氩元素,开启了发现稀有气体元素的历程,开辟了发现元素周期表中的零族元素之门。20世纪20年代氩元素同位素的发现使人们形成了对氩元素的概念的现代认知,同时英国化学家莫斯莱提出原子序数概念,揭示了元素在周期表中位置排列的实质,同氩同位素的发现相结合,解决了氩在周期表中的位置排列问题。20世纪上半叶原子结构和化学键理论的提出阻碍了氩化合物的发现。21世纪初,氟氩化氢的发现使人们对氩的“惰性”有了全新的认识,改称氩为稀有气体元素,并对化学键理论的发展起到促进作用。总之,氩元素概念的形成和发展对于元素周期律的完善和发展以及人们对原子结构和化学键理论的认识都起到了极为重要的桥梁作用。     

About the dependence of the intensity of X-ray spectra of elements on their concentrations expressed in atomic and mass percents

The consideration of the classical physical fundamentals of X-ray spectrometry suggests that the properties of X-ray spectra of elements are determined by their atomic number rather than atomic weight. The intensity of X-ray spectra is determined by the number of excited atoms rather by their mass. However, in the middle of the 20th century, the dependence of intensity on the mass concentration of elements was introduced without any physical grounds. The paper presents physical, analytical, and metrological evidences for the idea that this dependence does not correspond to a real physical process. It results in distorted calibration characteristics and extra errors and hinders the development of a method of universal (for all element systems) quantitative X-ray fluorescence analysis instead of specific procedures with empirical parameters for each particular system. The dependence on atomic concentrations eliminates these difficulties.     

论中学生化学元素观的建构

化学元素观是中学化学学习中的核心观念。化学元素观的建构有利于中学生对物质世界形成有序的认识,有利于中学生形成化学的思维方法。化学元素观建构的基本策略是:(1)在元素概念基础上形成物质的基本分类;(2)在原子结构认识的基础上理解元素是如何形成物质的;(3)在元素周期律学习的基础上形成元素性质研究的基本模型;(4)在专题性学习中建构化学元素观;(5)在元素观指导下的应用性学习中丰富元素观;(6)利用概念图技术帮助化学元素观的建构。     

铪元素及其同位素的发现：技术进步和思想发展的共同结晶

1869年，门捷列夫在第一张元素周期表中的锆元素后留出原子量为180的元素位置，预测铪与锆同族。1913年，原子序数和莫斯莱定律的提出揭示了铪元素在周期表中位置排列的实质，为铪元素的发现提供理论基础。20世纪20年代，玻尔理论的发展证实铪与锆同族，指导科学家从锆矿石中寻找铪元素。1923年，赫维西和科斯特借助X射线光谱技术发现铪元素，彰显了X射线光谱技术的独特价值。20世纪30年代以后，同位素理论和质谱技术促成了铪同位素的发现，使人们对铪元素有了新的认识。总之，铪元素及其同位素的发现是技术进步和思想发展的共同结晶。     

Informationsgehalt chemischer Elemente

The information approach for describing electronic structures of atoms was developed and different information characteristics of chemical elements were determined on this basis. The information functions display interesting features and correlate with the properties of chemical elements. The spin information of the elements having a closed electron shell, expressed in bits, was found to be equal to the atomic number of the element.

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Lavoisier and Mendeleev on the Elements

Lavoisier defined an element as a chemicalsubstance that cannot be decomposed usingcurrent analytical methods. Mendeleev saw anelement as a substance composed of atoms of thesame atomic weight. These `definitions' doquite different things: Lavoisier'sdistinguishes the elements from the compounds,so that the elements may form the basis of acompositional nomenclature; Mendeleev's offersa criterion of sameness and difference forelemental substances, while Lavoisier's doesnot. In this paper I explore the historical andtheoretical background to each proposal.Lavoisier's and Mendeleev's explicitconceptions of elementhood differed from eachother, and from the official IUPAC definitionof `element' of the 1920s. However, Lavoisierand Mendeleev both subscribed to – andemployed – a deeper notion of a chemicalelement as the component of compound substancesthat (i) can survive chemical change, and (ii)explains the chemical behaviour of itscompounds.     

张青莲教授及其原子量新值测定研究

张青莲教授是中国科学院院士,我国同位素化学的奠基人.本文介绍他在90高龄之际在原子量新值测定方面所取得的杰出成就.从1990年代初以来,他主持一个科研小组采用质谱法,实施了测定10项原子量新值的长期计划.至2001年7月已经有In、Ir、Sb、Eu、Ce、Er、Ge、Dy和Zn等9个原子量新值被国际纯粹与应用化学联合会(IUPAC)的原子量与同位素丰度委员会(CAWIA)正式确定为原子量的国际新标准;另外一个Sm原子量新值也于2005年被国际组织确认.     

元素原子量测量及其演进

2019年是门捷列夫发现元素周期表第150周年。本文从原子量概念的提出、原子量测量技术的发展、原子量测量的中国贡献、原子量新的表述形式的出现等方面系统回顾了在过往两百多年里元素原子量的发展历史。     

Measurements on thin sections of soils with the Eindhoven proton microprobe

In thin sections of soils inclusions of various sizes with various components and with different chemical composition are present. The chemical composition of these small inclusions can be measured with a proton microprobe using the SPIXE technique (Scanning Particle Induced X-Ray Emission). By scanning the thin section of soil with the Eindhoven proton microprobe (40 × 60 μm beam diameter) trace element mapping can be achieved with an optimum sensitivity of 20 ppm for elements with atomic number Z = 30(Zn). The result is shown with 1024 picture elements of a bauxite thin section.     

The possibility of constructing the hydrogen scale of the absolute atomic masses of the elements

The paper presents a scheme for the experimental-empirical construction of the existing chemical, physical, and carbon scales of the relative nonintegral atomic masses of the elements. The quantitative interrelation between the nonintegral relative atomic masses, their minimized fractional positive and negative natural deviations from integral numbers, and their integral parts are reproduced mathematically. Nonisotopic fractional deviations are shown to be a consequence of methodological side effects of the scheme for theoretical processing of the data of thorough physical and chemical measurements performed by Stas and Aston in constructing scales of relative atomic masses. In conformity with the Prout hypothesis, the absolute atomic mass unit and the corresponding Avogadro’s number value are suggested for the construction of the hydrogen scale of absolute atomic masses of nonisotopic elements, individual isotopes, and isotope-containing elements.     

What is an element? What is the periodic table? And what does quantum mechanics contribute to the question?

This article considers two important traditions concerning the chemical elements. The first is the meaning of the term “element” including the distinctions between element as basic substance, as simple substance and as combined simple substance. In addition to briefly tracing the historical development of these distinctions, I make comments on the recent attempts to clarify the fundamental notion of element as basic substance for which I believe the term “element” is best reserved. This discussion has focused on the writings of Fritz Paneth which are here analyzed from a new perspective. The other tradition concerns the reduction of chemistry to quantum mechanics and an understanding of chemical elements through their microscopic components such as protons, neutrons and electrons. I claim that the use of electronic configurations has still not yet settled the question of the placement of several elements and discuss an alternative criterion based on maximizing triads of elements. I also point out another possible limitation to the reductive approach, namely the failure, up to now, to obtain a derivation of the Madelung rule. Mention is made of some recent similarity studies which could be used to clarify the nature of ‘elements’. Although it has been suggested that the notion of element as basic substance should be considered in terms of fundamental particles like protons and electrons, I resist this move and conclude that the quantum mechanical tradition has not had much impact on the question of what is an element which remains an essentially philosophical issue.     

Prediction of the adsorption behavior of elements 112 and 114 on inert surfaces from ab initio Dirac-Coulomb atomic calculations

The interaction of elements 112 and 114 with inert surfaces has been studied on the basis of fully relativistic ab initio Dirac-Coulomb CCSD(T) calculations of their atomic properties. The calculated polarizabilities of elements 112 and 114 are significantly lower than corresponding Hg and Pb values due to the relativistic contraction of the valence ns and np(12) orbitals, respectively, in the heavier elements. Due to the same reason, the estimated van der Waals radius of element 114 is smaller than that of Pb. The enthalpies of adsorption of Hg, Pb, and elements 112 and 114 on inert surfaces such as quartz, ice, and Teflon were predicted on the basis of these atomic calculations using a physisorption model. At the present level of accuracy, -DeltaH(ads) of element 112 on these surfaces is slightly (about 2 kJ/mol) larger than -DeltaH(ads)(Hg). The calculated -DeltaH(ads) of element 114 on quartz is about 7 kJ/mol and on Teflon is about 3 kJ/mol smaller than the respective values of -DeltaH(ads)(Pb). The trend of increasing -DeltaH(ads) in group 14 from C to Sn is thus reversed, giving decreasing values from Sn to Pb to element 114 due to the relativistic stabilization and contraction of the np(12) atomic orbitals. This is similar to trends shown by other atomic properties of these elements. The small difference in DeltaH(ads) of Pb and element 114 on inert surfaces obtained within a picture of physisorption contrasts with the large difference (more than 100 kJ/mol) in the chemical reactivity between these elements.     

高压下的原子和分子行为

近些年,高压化学的研究取得了非常多的成果。本文从基础化学原理出发,讨论高压对原子轨道能量和化学键的影响。高压下,原子轨道能量会发生改变,从而导致核外电子在轨道间的重新排布,影响到元素的化学性质。于分子而言,高压下分子晶体会发生相变,不饱和化合物会发生自聚,饱和化合物则有可能金属化。     

Recent on-line processing procedures for biological samples for determination of trace elements by atomic spectrometric methods

Few of the elements present in nature play a metabolic role in living organisms. According to their abundance, these elements are classified as macro-, micro- or trace elements, representing 93%, 5% and around 1% respectively, of the total body weight. The remaining percentage could be attributed to those elements with unknown biological functions, to others which are present only because of the exposure to polluted environment or to those intentionally introduced into the body for a special treatment. This review summarizes and discusses the most recent publications related to the on-line processing of biological samples for trace element determination using atomic spectrometry-based detectors. Preconcentration/separation procedures based on solid phase or cloud point extractions, electrochemical deposition, microdialysis, as well as chemical vapor generation are the common practice for improving the sensitivity and selectivity of the available atomic spectrometric techniques. The advantages of using isotope dilution mass spectrometry in speciation studies are also emphasized. Digestion or leaching in oxidizing acidic mixtures aided by heat or by ultrasound or microwave radiation, performed off- or on-line, is necessary to previous steps when processing solid biological samples. The most relevant analytical figures of merit such as detection limits, enrichment factors and sample throughput as well as some aspects related to the on-line system configurations and accuracy assessments are critically presented.     

A century of progress in the sciences due to atomic weight and isotopic composition measurements

Even before the 20th century, a consistent set of internationally accepted atomic weights was an important objective of the scientific community because of the fundamental importance of these values to science, technology and trade. As the 20th century progressed, physicists, geoscientists, and metrologists collaborated with chemists to revolutionize the science of atomic weights. At the beginning of the century, atomic weights were determined from mass relationships between chemical reactants and products of known stoichiometry. They are now derived from the measured isotopic composition of elements and the atomic masses of the isotopes. Accuracy in measuring atomic weights has improved continually, leading to the revelation of small but significant variations in the isotope abundances of many elements in their normal terrestrial occurrences caused by radioactivity and a variety of physicochemical and biochemical fractionation mechanisms. This atomic-weight variability has now been recognized as providing new scientific insights into and knowledge of the history of materials. Atomic weights, except those of the monoisotopic elements, are thus no longer regarded as "constants of nature". At the beginning of the 20th century, two scales for atomic weights were in common use: that based on the atomic weight of hydrogen being 1 and that based on the atomic weight of oxygen being 16. Atomic weights are now scaled to (12)C, which has the value 12 exactly. Accurate atomic weights of silicon, silver, and argon, have enabled the values of the Avogadro, Faraday and Universal Gas constants, respectively, to be established, with consequent effects on other fundamental constants.     

Speciation of oxidation states of elements by capillary electrophoresis

Progress made in the last five years in the application of capillary electrophoresis methods to chemical speciation of elements is reported on the basis of over 100 literature references. The main trends observed include development of new on‐ and off‐capillary derivatization methods, application of new detection methods, and especially coupling of CE separation systems to powerful atomic spectroscopy and mass spectrometry instruments with various ionization techniques, providing either a sensitive element‐specific detection method or a third dimension for high performance separation. Besides numerous CZE and MEKC capillary electrophoresis methods only very few examples of CE speciation with capillary electrochromatography can be found. Concerning the chemical forms of elements determined, the new procedures developed are mostly focused on redox speciation of various oxidation states of elements, metal‐bound high molecular compounds, and organometallic species.     

Ma?systeme in der quantitativen analytischen organischen Chemie

Zusammenfassung Es wird ein einheitliches Maßsystem für die organisch-chemische funktionelle Gruppenanalyse vorgeschlagen. Dieses paßt sich den heutigen Bedingungen, speziell der kombinierten Anwendung physikalischer und chemischer Analysenverfahren zwanglos an und fördert die Kontrolle der Richtigkeit analytischer Werte. Der Meßwert heißt Funktionszahl, er gibt die Gewichts-% (oder Gewichts-ppm) des Schlüsselelements der funktionellen Gruppe an und ergibt sich aus F=Milliäquivalent·0,1·Atomgewicht Schlüsselelementsumme/g ProbeSchlüsselelement in gemischten funktionellen Gruppen ist das in der Reihe C-O-N-S-Hal am weitesten rechts stehende bzw. das sonst entscheidende Element. Schlüsselelement der O-Gruppen ist demnach O, der N-haltigen Gruppen N, der S-haltigen Gruppe S usw.

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Summary A new scale (system of measures) capable of uniformly expressing results of quantitative organic functional group analysis is proposed. It is especially adapted to the modern trend of combined application of physical and chemical methods. It facilitates the comparison of results derived from these different methods and consequently helps to control their accuracy. This value is called functional number. It gives the weight percent of the so-called functional element in the respective functional group: F=meq×0.1×n× atomic weight of functional elements/g meq/g=milliequivalent of functional group per g of sample n=number of same functional element in the group (-COOR: n for O=2).Functional element in mixed functional groups is the most important one; the following order should be observed: Hal-S-N-O-C.

     

软硬酸碱理论与元素的存在形式

在无机化学元素部分教学中,元素的存在形式既是该元素化学性质的重要组成部分,又决定了元素单质和化合物的制备与合成方法。运用离子的电子结构知识及化学基本原理分析元素在自然界中的存在形式,既可以加深学生对化学基本知识和基本原理的理解,又可以将元素知识形成知识链以减少记忆量。本文利用软硬酸碱理论和地球环境的基本状况来分析元素在自然界的存在形式,得到了与实际较为符合的结果,表明这是一种简单实用的思路和方法。     

钛元素的发现及其概念发展

1791年,英国矿物学家格雷戈尔发现钛矿石并意识到一种新元素的存在。至1795年,普鲁士化学家克拉普罗特进一步预言了该元素,并将之正式命名为钛(Titanium)。1910,美国化学家亨特制取了纯净的钛单质,钛元素的概念正式形成。20世纪20年代以后,钛同位素的发现使人们对钛元素概念有了新认识,并逐渐形成现代钛元素概念。钛元素概念的发展使人们在科学认知上发生了转变,促进了化学元素观的演进。