Photoemissionsspektroskopie in Chemie und Physik

The principles of photoemission spectroscopy and of its application to problems in chemistry and physics are discussed. Examples will be presented for atoms, molecules, solids and surfaces. The following topics will be discussed: binding energies of core levels (rare gases), binding energies of valence levels (CO), analysis of a valence band spectrum in terms of MO-calculations (C₆H₆), core polarization (O₂), chemical shift (O), plasmon excitations (Be-metal), energy dispersion relations for a solid (Cu), exchange splitting in a metal (Ni), surface states (Si), energy levels of adsorbates (Ni on Au, C₆H₆ on Ni).     

Myonische Atome in Physik,Chemie und Archäometrie

A survey is given of properties, formation, and application of muonic atoms in physics, chemistry, and archeometry. In the field of physics the measurement of nuclear charge distributions and vacuum polarization as well as the slowing down of muons in matter are treated in some detail, and in the fields of chemistry and archeometry, non-destructive quantitative chemical analysis of bulk material and, with the help of suitable beam setting, also of selected parts of the specimen.     

The nitrate radical: Physics,chemistry, and the atmosphere

This review surveys the present state of knowledge of the nitrate (NO₃ radical. Laboratory data on the physics and chemistry of the radical and atmospheric determination of the concentrations of the radical are both considered. One aim of the review is to highlight the relationship between the laboratory and the atmospheric studies. Although the emphasis of the review is on gas-phase processes, relevant studies conducted in condensed phases are mentioned because of their potential importance in the interpretation of cloud and aerosol chemistry.The spectroscopy, structure, and photochemistry of the radical are examined. Here, the object is to establich the spectroscopic basis for detection of the radical and measurement of its concentration in the laboratory and in the atmosphere. Infrared, visible, and paramagnetic resonance spectra are considered. An important quantity discussed is the absorption cross section in the visible region, which is required for quantitative measurements. Interpretation of the spectroscopic features requires an understanding of the geometrical and electronic structure of the radical in its ground and excited states; there is still some controversy about the groundstate geometry, but the most recent experimental evidence 9eg from laser induced fluorescence) and theoretical calculations suggest that the radical has D_3h symmetry. Photodissociation of the radical is important in the atmosphere, and the product channels, quantum yields, and dissociation dynamics are discussed. A short examination of the thermodynamics (heat and entropy of formation) of the radical is presented.The main exposition of laboratory studies of the chemistry of the nitrate radical is preceded by a consideration of the techniques used for kinetic and mechanistic studies. Methods for the generation and detection of the radical and the kinetic tools employed are all presented. The exact nature of the technique used in individual studies has some relevance to the way in which data must be analysed, and to the type of mechanistic information that can be extracted. Continuous and stopped flow, flash photolysis and pulse radiolysis, molecular modulation, and static reactor techniques can all provide absolute kinetic data, while relative rate measurements have been a further rich source of information.The treatment of the chemical reactions of the nitrate radical is formally divided into the interactions with non-radical inorganic (deemed to include NO and NO₂) and organic species, and with atoms and free radicals. In general, the reactions with open-shell species are much more rapid than those with closed-shell reactants. With the closed-shell partners, addition reactions are faster than abstraction reactions. An attempt is made to consider critically the published data on most reactions of importance, and to tabulate rate constants and temperature dependences where possible. However, it is not the objective of this review to provide recommendations for rate parameters. Evidence for the products of the reactions is sought, and for the branching ratios into the various channels where more than one exists. One theme of this part of the review is the elucidation of correlations of reactivity with structure and with the reactions of other radical species such as OH.The review turns next to a consideration of the role of NO₃ in the atmosphere, of its atmospheric sources and sinks, and of field measurements of concentrations of the radical. Long-path visible-absorption spectroscopy and matrix-isolation ESR have both been used successfully in field measurements in the troposphere as well as the stratosphere. Balloon-borne instruments and ground-based remote sensing have been used to obtain stratospheric concentrations. Two of the most important implications of the measurements are that the stratospheric profiles are consistent with accepted chemistry (and, in particular, do not require the postulation of an unidentified scavenging mechanism that had, at one stage, been proposed), and that the highly variable night-time tropospheric concentrations imply that NO₃ is a reactive tropospheric constituent. The inter-relation between laboratory studies and atmospheric observations, and the problems in extrapolating laboratory data to atmospheric conditions, are both explored. Initiation of night-time chemical transformations by NO₃ and the possible production of OH are considered. The available information is then brought together to see how far NO₃ is a sensitive indicator of the state of the atmosphere, and some speculations are presented about the involvement of NO₃ (or N₂O₅) in damage to trees and plants.The final section of the review suggests some issues that remain unresolved concerning the NO₃ radical which is directly or indirectly relevant to a better knowledge of the part played by the radical in the atmosphere. Amongst the requirements noted are improved data for the heat of formation of the radical, its absorption cross section in the visible region (and, especially, the temperature dependence of the cross section), and the details of its photochemistry. There is also still a need for a definitive determination of the equilibrium constant and its temperature dependence for the association with NO₂ and the reverse dissociation of N₂O₅. A series of chemical reactions deserves further investigation, especially with regard to elucidation of product channels, and overall oxidation mechanisms also need to be defined better. Future atmospheric studies that are desirable include study of basic NO₃ chemistry in the field to understand the influence of humidity on the conversion (probably on surfaces) of N₂O₅ to HNO₃, and thus on NO₃ concentrations. In addition, a study of the chemistry of NO₃ in the presence of volatile organic compounds and at elevated concentrations of the oxides of nitrogen should help in the understanding of, for example, polluted marine coasts, forests, and urban areas.     

Aluminum position in Rb-feldspar as determined by X-ray photoelectron spectroscopy

Al/Si configurations in some natural and synthetic Rb-feldspars have been examined carefully by EMPA and XPS analyses. Our results indicate that a small amount of H₂O and excess Si and Al are incorporated in hydrothermally synthesized Rb-feldspar. The quantities of excess Al are 0.056 atoms per formula unit and are negatively correlated with those of the Rb, suggesting the presence of excess Al occupying non-tetrahedral sites in feldspar structures. This leads to incorporation of Al(Al₃Si)O₈ endmember into Rb-feldspars, estimated as one appropriate endmember indication for unusual chemistry of feldspars. In addition, Si2p, Al2p and O1s XPS signals of Rb-feldspars shift drastically toward the higher energy side than those of any natural feldspars. These provide conclusive evidence not only for existence of perceptible excess Si and Al, but also for Al at both extra-framework and tetrahedral sites in feldspar structures.     

大气气溶胶中碘形态研究进展

大气中的碘直接影响对流层中多种光化学反应并间接影响全球气候变化,因而碘的大气化学机制研究受到越来越多关注.气溶胶中的碘是其大气化学反应的最终产物,通过其赋存形态可以推测和了解碘的大气化学过程.大气碘化学理论一直认为IO3-是大气碘沉降中最主要的碘形态,但近年来的各地实测数据发现大气气溶胶中的碘形态大多以可溶性有机碘或I-为主.这种分歧说明目前的大气碘化学理论尚有待完善.本文详细介绍了近年来碘的大气化学以及气溶胶颗粒物中碘形态的研究进展.     

Organic peroxy radicals: Kinetics,spectroscopy and tropospheric chemistry

The present state of knowledge of organic, or carbon-based, peroxy radicals (RO₂) is reviewed. Data on the chemical and physical properties of peroxy radicals in the gas-phase is considered, as well as the role of peroxy radicals in tropospheric chemistry and measurements of their concentrations in the atmosphere. Where appropriate, peroxy radicals are grouped together by type (alkyl, acyl, oxygen-substituted, halogen-substituted and aromatic radicals) to facilitate comparison. Data on the hydroperoxy radical (HO₂) is included where it is directly relevant to measurements on organic peroxy radicals, eg. absorption cross-sections used in measurements of RO₂ + HO₂ rate constants. The literature data is critically reviewed and recommendations for absorption cross-sections, rate constants and branching ratios are made where considered appropriate.The laboratory experimental techniques which have been used for the generation and detection of peroxy radicals and the products of their reactions are discussed. The structure, spectroscopy and thermochemistry of the radicals are examined. Although the majority of spectroscopic data concerns the u.v. spectra much used for kinetic studies, near-infrared, infrared and electron spin resonance spectra are also considered. In many cases, peroxy radical u.v. spectra are well-fitted by a Gaussian distribution function, enabling the cross-sections to be easily calculated at any wavelength.For the purpose of this review, the chemical reactions of peroxy radicals are divided into reactions with organic peroxy radicals with HO₂, with NO and NO₂, and finally with other species. Peroxy radical abstraction and addition reactions with closed-shell species are sufficiently slow to be of negligible importance at temperatures pertinent to the atmosphere and are consequently not covered. Data on both the kinetics and mechanisms of peroxy radical reactions are considered.The role of peroxy radicals as intermediates in the atmospheric degradation of volatile organic compounds and in the production of ozone in the troposphere under both low and high [NO_x] conditions is discussed. The involvement of peroxy radicals in night-time oxidation chemistry and the oxidation of halocarbons is also indicated. The techniques used for the difficult measurement of peroxy radical concentrations in the atmosphere are described, together with the results to date.Finally, some tentative suggestions as to further avenues of research are made, based on the data reviewed here and with particular reference to the solution of outstanding problems in atmospheric chemistry. Although a great deal of progress has been made in recent years, it is clear that additional work is needed in most areas covered by this review. New, sensitive and selective laboratory techniques are required for studies of peroxy radical kinetics and high level ab initio calculations would help design laser-based detection techniques. Further product studies of photooxidation systems are needed, particularly as a function of temperature. Recent work has shown that the rate constants for RO₂ + HO₂ reactions used in modelling studies may be too low; if so, these reactions will be correspondingly more important than previously believed in tropospheric oxidation. Recent kinetic studies of the potentially important reactions of methylperoxy radicals with ClO and NO₃ need to be confirmed and mechanistic work is necessary. Although substantial progress has been made towards the monitoring of peroxy radical concentrations in the atmosphere, more work is needed, both on measurements and the development of new techniques.     

Chemistry and physics of amorphous semiconductors

Our understanding of amorphous semiconductors has been greatly clarified by recent theoretical and experimental work. It is now evident that the electrical properties of these materials are generally controlled by intrinsic defects which are either thermodynamically required or induced via strains during the deposition process. The nature of these defects is intimately related to the chemistry of the constituent atoms.     

Gas separation using porous cement membrane

Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subject. CO2 capture and storage have important roles in ＂green chemistry＂. As an effective clean technology, gas separation using inorganic membranes has attracted much attention in the last several decades. Membrane processes have many applications in the field of gas separation. Cement is one type of inorganic material, with the advantages of a lower cost and a longer lifespan. An experimental setup has been created and improved to measure twenty different cement membranes. The purpose of this work was to investigate the influence of gas molecule properties on the material transport and to explore the influence of operating conditions and membrane composition on separation efficiency. The influences of the above parameters are determined, the best conditions and membrane type are found, it is shown that cementitious material has the ability to separate gas mixtures, and the gas transport mechanism is studied.     

城市环境PM2.5空间分布监测方法研究进展

随着城市化和工业化的发展,城市环境中日益增多的PM_(2.5)对人类健康造成了严重威胁。本文旨在分析总结目前PM_(2.5)空间分布的相关监测方法以及空气质量预测模型。当下,PM_(2.5)浓度的监测不仅涉及大气化学、污染物的源解析、大气化学运输模型、线性及非线性空气质量模拟等方面,还涉及地理信息系统与卫星遥感等新技术的运用。本文在比较传统PM_(2.5)监测与新型监测方法不同的基础上,分析了各自的优劣,为空气质量监测提供建议和指导。     

Mexico City and the biogeochemistry of global urbanization

Mexico City is far advanced in its urban evolution, and cities in currently developing nations may soon follow a similar course. This paper investigates the strengths and weaknesses of infrastructures for the emerging megacities. The major driving force for infrastructure change in Mexico City is concern over air quality. Air chemistry data from recent field campaigns have been used to calculate fluxes in the atmosphere of the Valley of Mexico, for compounds that are important to biogeochemistry including methane (CH₄), carbon monoxide (CO), nonmethane hydrocarbons (NMHCs), ammonia (NH₃), sulfur dioxide (SO₂), nitrogen oxides (NO_x and NO_y), soot, and dust. Leakage of liquified petroleum gas approached 10% during sampling periods, and automotive pollutant sources in Mexico City were found to match those in developed cities, despite a lower vehicle-to-person ratio of 0.1. Ammonia is released primarily from residential areas, at levels sufficient to titrate pollutant acids into particles across the entire basin. Enhancements of reduced nitrogen and hydrocarbons in the vapor phase skew the distribution of NO_y species towards lower average deposition velocities. Partly as a result, downwind nutrient deposition occurs on a similar scale as nitrogen fixation across Central America, and augments marine nitrate upwelling. Dust suspension from unpaved roads and from the bed of Lake Texcoco was found to be comparable to that occurring on the periphery of the Sahara, Arabian, and Gobi deserts. In addition, sodium chloride (NaCl) in the dust may support heterogeneous chlorine oxide (ClO_x) chemistry. The insights from our Mexico City analysis have been tentatively applied to the upcoming urbanization of Asia.     

喜马拉雅东段错那地区雪中主要离子年际变化及来源分析

雪中阴阳离子化学记录可以提供关于大气环流、气候和环境变化的信息,喜马拉雅山因其独特的位置和丰富的冰川资源成为研究雪化学的重要地区。本论文基于两个年度(2018年2～3月和2018年12月～2019年1月)在喜马拉雅东段错那地区采集的新雪样品,对雪中主要离子的组成和浓度特征的年际变化进行分析,并结合相关分析法、海盐示踪法和气团后向轨迹法对其来源进行研究。结果表明,错那地区两年度雪中主要阳离子均为Ca²⁺,主要阴离子均为SO^2-₄。受2019年强降雪清除作用的影响,2019年度各离子的浓度明显低于2018年度。错那地区雪中Ca²⁺的含量明显高于喜马拉雅山其他研究区域,可能是由于其海拔较低,受近源陆地粉尘影响较大。离子来源分析结果表明,错那地区雪中离子以局地陆源物质输入为主,部分来源于海洋源(Cl^-、Na⁺)、盐湖矿物风化(Cl^-、Na⁺、K⁺和SO^2-₄)以及人为源(NH⁺₄、NO^-₃、SO^2-₄)。本文可为错那地区生态建设管理及喜马拉雅地区的雪化学和大气环流特征研究提供参考。     

岩溶槽谷石漠化治理区表层泉水化学特征研究:以重庆酉阳泔溪花椒基地老泉为例

背斜型岩溶槽谷区石漠化治理的关键之一是要厘清地下水资源动态变化特征,尤其要开展在线高分辨率连续动态监测。本文以重庆酉阳龙潭岩溶槽谷石漠化治理区老泉监测站为例,采用PONSEL多参数自动记录仪现场测定和样品室内分析相结合的方法,研究老泉2017年完整水文年的季节和强降雨期间的水化学动态特征,利用主成分分析法探究季节尺度和强降雨期间老泉水化学组分的主要来源。结果表明：（1）在季节尺度上,受雨水稀释作用的影响,雨季泉水pH、电导率、Ca²⁺、HCO₃^-、Mg²⁺低于旱季;土壤受淋溶作用的影响,泉水K⁺、Na⁺、全Mn、Al³⁺、全Fe浓度雨季高于旱季;水化学变化主要受4个主成分影响,累计贡献率为85.53%,但主导要素是水岩作用及土壤元素流失;（2）强降雨期间,石漠化背景下泉水水化学指标对降雨响应迅速,但在植被不同生长状态下各指标差异明显;典型的两次强降雨过程中水化学变化都主要受4个主成分影响,累计贡献率分别为85.63%和85.40%,但主导要素是农业活动和土壤元素流失;（3）花椒树种植后泉水中NO₃^-、SO₄^2-质量浓度较高,且硫酸和硝酸参与岩溶作用过程并对老泉水质造成重要影响。因此,背斜型岩溶槽谷表层泉水化学特征的监测研究,对于槽谷石漠化治理区水资源高效利用具有重要现实意义。     

Degradation of monofluorophenols in water irradiated with gaseous plasma

Decomposition of aqueous monofluorophenols (MFPs) was investigated by contact glow discharge electrolysis (CGDE). During CGDE, both MFPs and the corresponding total organic carbon (TOC) in water were consumed smoothly, suggesting that carbon atoms of benzene nucleus could be eventually mineralized to inorganic carbon (IC). And all the fluorine atoms in the MFPs were equally converted to fluoride ions. Based on the primary intermediates from each starting materials, it showed that aromatic hydroxylation preferentially occurred at the para- or ortho- position to the phenolic OH group of each MFPs. The disappearance of both MFPs and TOC followed the first-order rate law. The apparent rate constants for the decay of MFPs were independent from the pK_a values of MFPs.     

Degradation of monofluorophenols in water irradiated with gaseous plasma

Decomposition of aqueous monofluorophenols (MFPs) was investigated by contact glow discharge electrolysis (CGDE). During CGDE, both MFPs and the corresponding total organic carbon (TOC) in water were consumed smoothly, suggesting that carbon atoms of benzene nucleus could be eventually mineralized to inorganic carbon (IC). And all the fluorine atoms in the MFPs were equally converted to fluoride ions. Based on the primary intermediates from each starting materials, it showed that aromatic hydroxylation preferentially occurred at the para-or ortho-position to the phenolic OH group of each MFPs. The disappearance of both MFPs and TOC followed the first-order rate law. The apparent rate constants for the decay of MFPs were independent from the pK_a values of MFPs.     

Density functional and experimental study of NO/O2 on zigzag char

In this paper, quantum chemistry computation (density functional theory) of multi-air-staged combustion was investigated in combination with experiment. It was found that the presence of oxygen in the combustion environment has a great influence on the surface chemistry of coal char. In the reaction pathway, the ring-opening reaction happens first, and is followed by NO adsorption. Afterwards, the ring-closure reaction takes place, leaving the nitrogen atom trapped in the inner char molecule. This reaction route effectively inhibits NO formation and achieves the aim of controlling NO emissions. In the staged combustion experiments, the consumption of O₂/NO was accompanied by an increase in the CO₂ concentration. The quantum chemistry computation successfully interprets the recent experimental trends displayed in multi-air-staged combustion.     

石灰石和菱镁矿对酸化森林土壤修复作用的研究

以重庆铁山坪马尾松林下典型的酸化土壤为修复介质,将土壤溶液pH值和主要阴阳离子浓度作为测试指标,对石灰石和菱镁矿这2种化学修复剂的修复效果进行了为期1a的野外实验研究.结果表明:与未投加修复剂的土壤相比,投加石灰石和菱镁矿后土壤溶液的pH值和相应阳离子(Ca²⁺或Mg²⁺)浓度显著上升,而且无机单体铝(Al_i)浓度明显下降,从而起到了缓解土壤酸化并降低其对植被危害的效果.但是,修复剂的投加导致NO₃^{-相似文献}   

金华江城区段河流水化学变化及其控制因素

为揭示金华江城区段河流水化学变化及其控制因素,从2015年8月到2016年6月对金华江城区段进行了连续11个月的采样分析,并结合当地降水等数据,得到以下结论:(1)金华江城区段河水p H值的变幅为6.80~7.70,呈现中性,电导率EC的变化范围较大,流域TDS含量低于世界河水平均值,流域阳离子以Ca~(2+)为主,阴离子以HCO_3~-为主,河水水化学类型为HCO_3~--Ca~(2+)型;(2)主要离子浓度具有明显的季节变化特征,总体上呈现出夏季低、冬季高的特点,Cl~-浓度变化与降水量变化具有一致性;(3)水化学控制因素以岩石风化为主,但也有向大气降水控制型过渡的趋势,人类活动对河流水化学也产生了很大影响。     

甘肃武山地热田水化学与地热水起源

通过对武山地热田地热水和地下冷水的水化学和同位素分析,结果表明武山地热水的出露温度为18.2~42.1℃,TDS含量为238~255 mg/L,属于低矿化度的HCO3型水。相对于地下冷水,地热水有更高的S iO2、F含量,说明经历了比冷水更长的循环深度。水化学特征表明武山地热水为大气降水与岩石相互作用的初级阶段。武山冷水和地热水的同位素沿着西北大气降水线分布,由于地热水的水岩相互作用时间较长,有更低的δD和δ18O值,说明武山地热水是大气来源的。综合运用各种地热温标估算武山地热水的热储温度范围在70~106℃之间,按照甘肃东部的平均地温梯度(35℃/km),得出武山地热水循环深度为1.74~2.77 km,属于中低温地热系统。此研究为今后可持续开发武山地热水提供了科学依据。     

Hydrogen peroxide levels in Los Angeles: A screening-level evaluation

The major factors affecting the diurnal variation of gaseous hydrogen peroxide were studied using a one-dimensional vertical gas-phase chemistry/transport screening model. The model which included diurnal variations of the inversion layer, surface emissions, dry deposition of air pollutants, and meteorological conditions such as solar radiation, temperature, relative humidity and wind speed, was used to evaluate the influence of the ratio of NMHC/NO_x, the emission rates of NO_x and NMHC, the deposition velocity of H₂O₂, and the height of inversion layer on the ground level gaseous H₂O₂ concentrations. The model was found to yield reasonable agreement with field data from the Carbonaceous Species Methods Comparison Study at Glendora, California, in 11–21 August 1986. Specifically, model predictions and field results all indicated that during clear skies, ambient H₂O₂ concentration was highest at about early afternoon when O₃ concentration was highest and NO_x was lowest. It was concluded that the predicted gaseous H₂O₂ concentration is most sensitive to the emission rate of NO_x and the ratio of NHMC/NO_x, but it is less sensitive to the deposition velocity, height of inversion layer, and the emission rate of NMHC.