催化光度法测定水中的痕量NO2-

基于磷酸介质中亚硝酸根催化溴酸钾氧化靛蓝胭脂红的褪色反应,建立了测定水中痕量亚硝酸根的催化光度法,并利用正交试验对测定方法进行了优化,亚硝酸根的检测限为1.36×10~(-6)g/L,线性范围为0.3～2.0 μg/25mL。该法用于蔬菜及环境水样中痕量亚硝酸根的测定,结果准确。     

裂解气中痕量杂质的测定

应用色谱-质谱联用仪（GC-MS）研究了裂解气中痕量NO、AsH3、COS、硫醇、硫醚、甲醇等杂质的分析方法,研究结果表明该法具有灵敏度高、选择性好的特点,可为裂解气的利用研究提供可靠的数据,经过改进后还有可能被乙烯和丙烯生产厂用作乙烯或丙烯中痕量杂质分析的常规方法。     

化学蒸气发生-原子荧光光谱法测定水中痕量Hg的影响因素探讨

化学蒸气发生-原子荧光光谱法(CVG-AFS)是一种痕量和超痕量的分析方法,具有测定灵敏度高、检出限低的特点。测汞时由于汞离子可以与硼氢化钾(钠)生成原子态的汞,在“冷”条件下可被激发出汞的原子荧光,一般也被称为冷原子蒸气法。笔者以海光AFS-2202型双道原子荧光光度计为例,就分析过程中可能出现的几种影响因素进行分析,并提出消除办法。1试剂空白的影响试剂空白值对分析方法的检出限和测定结果的准确度、精密度有着较大的影响。要求检测汞的量通常都是痕量级,空白值过高,所出现的荧光信号要比正常情况高出许多,这将直接影响到样品(特…     

The coulometric determination of chemical oxygen demand

The chemical oxygen demand (COD) of solutions containing various organic compounds is calculated from the net faradaic charge (Q_net) estimated for the total electrolytic oxidation of Cr^III generated during oxidative degradation of the organic compounds in acidic media containing excess Cr^VI. Values of Q_net for conversion of Cr^III to Cr^VI are estimated from the linearized chronoamperometric data plotted as In {i_{tat, t}} vs. t. This procedure is preferred over determinations of Q_net from the total integrals of i_tot over the entire electrolysis period because of large errors that can result from uncertainty in the background current (i_bkg) for t → ∞. The proposed coulometric procedure offers the benefit that reagent solutions can be reused, thereby minimizing the need for disposal of wastes containing toxic Cr^VI. This procedure was applied in a single digest solution for consecutive determinations of COD. Average COD values for potassium acid phthalate and glucose were 103.8% (s - 6.0, N - 10) and 100.2% (s - 4.2, N - 11), respectively, based on the theoretical degradation to CO₂. In comparison for these same samples, an EPA approved method, based on colorimetric determination of Cr^III, gave COD values of 101.4% (S - 1.4, N - 5) and 100.1% (s - 1.4, N - 5) of the theoretical. Statistical tests indicate no significant difference in the COD values determined for these compounds using the coulometric and EPA methods.     

三效催化剂作用下的NO+CO催化反应机理

NO与CO在Pt/Rh/Pd及载体组成的三效催化剂上的氧化还原应用是控制汽车尾气对空气污染的一个关键反应，这一反应随着近年来对环境保护的日益重视而成为国内外研究的热点，本文主要综述了NO及CO在Pt,Rh,Pd上的吸附及反应机理的实验及理论研究现状，总结得出：在三效催化剂对NO CO的催化反应中，Pt,Pd对CO的催化氧化起主要作用，而Rh对NO的解离有很好的活化作用。     

Electrocatalytic Synthesis of Pyridine Oximes using in Situ Generated NH2OH from NO species on Nanofiber Membranes Derived from NH2-MIL-53(Al)

Pyridine oximes produced from aldehyde or ketone with hydroxylamine (NH₂OH) have been widely applied in pharmaceutics, enzymatic and sterilization. However, the important raw material NH₂OH exhibits corrosive and unstable properties, leading to substantial energy consumption during storage and transportation. Herein, this work presents a novel method for directly synthesizing highly valuable pyridine oximes using in situ generated NH₂OH from electrocatalytic NO reduction with well-design nanofiber membranes (Al-NFM) derived from NH₂-MIL-53(Al). Particularly, 2-pyridinealdoxime, the precursor of antidote pralidoxime (2-PAM) for nerve agents suffering from scarcity and high cost, was achieved with a Faraday efficiency up to 49.8 % and a yield of 92.1 %, attributing to the high selectivity of NH₂OH production on Al-NFM, further easily reacted with iodomethane to produce 2-PAM. This study proposes a creative approach, having wide universality for synthesizing pyridine and other oximes with a range of functional groups, which not only facilitates the conversion of exhaust gas (NO) and waste water (NO₂⁻) into valuable chemicals especially NH₂OH production and in situ utilization through electrochemistry, but also holds significant potential for synthesis of neuro detoxifying drugs to humanity security.     

Recent progress in catalytic NO decomposition

Recent progress in catalytic direct NO decomposition is overviewed, focusing on metal oxide-based catalysts. Since the discovery of the Cu-ZSM-5 catalyst in the early 1990s, various kinds of catalytic materials such as perovskites, C-type cubic rare earth oxides, and alkaline earth based oxides have been reported to effectively catalyze direct NO decomposition. Although the activities of conventional catalysts are poor in the presence of coexisting O₂ and CO₂, some of the catalysts reviewed in this article possess significant tolerance toward these coexisting gases. The active sites for direct NO decomposition are different depending on the types of metal oxide-based catalysts. In the case of perovskite type oxides, oxide anion vacancies act as catalytically active sites on which NO molecules are adsorbed. C-type cubic rare earth oxides contain oxide anion vacancies with large cavity space, enabling easy access of NO molecules and their subsequent adsorption. Surface basic sites on alkaline earth based oxides participate in NO decomposition as active sites on which NO molecules are adsorbed as NO₂⁻ species. The reaction mechanisms of direct NO decomposition are also discussed.     

Voltammetric determination of As(III) in an aqueous zwitterionic complexing medium

Summary The polarographic behaviour and determination of As(III) in aqueous complexing electrolytes (bicine buffer solutions) ofpH values varying from 1.13–11.96 have been investigated at 25°C (direct current and differential pulse polarographic techniques). Using DC polarographic measurements, it was shown that reduction of As(III) takes place along one or three waves depending upon thepH value of the solution. Microcoulometric experiments have been performed at the limiting region of the different waves obtained at differentpH values. Cyclic voltammograms were recorded using a HDME to investigate the nature of reduction. Schemes for the mechanism of reduction occurring at the DME have been deduced. Kinetic parameters and wave characteristics for the reduction of As(III) have been calculated. A method for DPP determination of As(III) in bicine buffer solution ofpH 1.41 is reported. The detection limit of the method is 6.60×10^–8 M As(III).

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Voltammetrische Bestimmung von As(III) in einem wäßrigen zwitterionischen komplexierenden Medium

Zusammenfassung Das polarographische Verhalten und die polarographische Bestimmung von As(III) in wäßrigen komplexierenden Elektrolyten (Bicin-Pufferlösungen) wurde beipH-Werten zwischen 1.13 und 11.96 und 25°C untersucht (Direktstrom- und Differentialpulstechniken). Mittels DC-Polarographie wurde gezeigt, daß die Reduktion von As(III) je nach dempH-Wert der Lösung in einer oder in drei Wellen erfolgt. In den Grenzbereichen der bei verschiedenenpH-Werten erhaltenen unterschiedlichen Wellen wurden microcoulometrische Experimente durchgeführt. Zur Untersuchung des Reduktionsvorgangs wurden cyclische Voltammogramme unter Verwendung einer HDME durchgeführt. Für den Mechanismus der an der Quecksilbertropfelektrode stattfindenden Reduktion wurden Reaktionsgleichungen ermittelt. Kinetische Parameter und Wellencharakteristika für die Reduktion von As(III) wurden berechnet. Eine Methode zur Bestimmung von As(III) mittels differentieller Pulspolarographie in Bicin-Pufferlòsung beipH 1.14 wird vorgestellt. Die Erfassungsgrenze der Methode liegt bei 6.60×10^–8 M As(III).

     

Three-step extraction procedure for determination of heavy metals availability to vegetables

A three-step sequential extraction procedure was used to determine the concentration of heavy metal speciation forms in soil. The procedure allows one to identify the pool of heavy metals that can be potentially mobilised under changes in soil pH value or redox potential. It has been shown that similar portions of heavy metals are present in reducible, oxidisable and residual fractions. It was found that soil chemical properties significantly affected the distribution of heavy metals among different fractions and their uptake by vegetables. Cadmium was a dominant element which occurred in the exchangeable fraction—the most bioavailable and potentially toxic.     

Thin layer coulometric determination of nitrate in fresh waters

A nitrate ion-selective electrode (ISE) employing a permeable tubular membrane impregnated with a conventional ISE cocktail has been used successfully in the coulometric analysis of nitrate in fresh waters. The liquid ISE membrane comprising a nitrate ionophore [tridodecylmethylammonium nitrate (TDMAN)], lipophilic electrolyte [tetradodecyl-ammoniumtetrakis(4-chlorophenyl)borate (ETH 500)] and plasticizer [bis(3-ethyl-hexyl)sebacate (DOS)] was supported on a porous polypropylene tube. Coulometric analysis with the tubular membrane ISE showed that nitrate could be detected in the range 10–100 μM with a precision of 2.3% relative standard deviation (RSD), limit of detection of 1.1 μM and relative accuracy of 4.4% compared to a certified reference material (CRM) Lake sample.     

Coulometric determination of total sulfur and reduced inorganic sulfur fractions in environmental samples

Evaluation of the solid-phase partitioning of sulfur is frequently an important analytical component of risk assessments at hazardous waste sites because minerals containing reduced-sulfur can significantly affect the transport and fate of organic and inorganic contaminants in natural environments. We applied selected methods for the determination of total sulfur, acid-volatile sulfide (AVS), chromium-reducible sulfur (CRS), and extractable-sulfate in standard reference materials and sediment samples from a contaminated site. A coulometric titration method is presented and evaluated for total sulfur, AVS, and CRS. This method is especially advantageous for AVS and CRS determinations because hydrogen sulfide gas evolved during chemical extraction is detected and quantitated in-line; consequently, measurement endpoints can be precisely determined without need for setting arbitrary time limits. The coulometric method allows for improved data quality and increased laboratory throughput of samples. Data on sulfur partitioning are presented for four standard reference materials (NIST 1646a, NIST 2780, CCRMP LKSD-1, CCRMP RTS-3) for the purpose of supporting quality control in environmental studies involving the geochemical and biochemical cycling of sulfur.     

Potentiometric determination of the total acidity of humic acids by constant-current coulometry

A straightforward method for both the quantitative and the equilibrium analysis of humic acids in solution, based on the combination of potentiometry with coulometry, is presented. The method is based on potentiometric titrations of alkaline solutions containing, besides the humic acid sample, also NaClO₄ 1 M; by means of constant current coulometry the analytical acidity in the solutions is increased with a high precision, until the formation of a solid phase occurs. Hence, the total acid content of the macromolecules may be determined from the e.m.f. data by using modified Gran plots or least-squares sum minimization programs as well. It is proposed to use the pK_w value in the ionic medium as a check of the correctness of each experiment; this datum may be readily obtained as a side-result in each titration. Modelling acid-base equilibria of the HA samples analysed was also performed, on the basis of the buffer capacity variations occurring during each titration. The experimental data fit, having the least standard deviation, was obtained assuming a mixture of three monoprotic acids (HX, HY, HZ) having about the same analytical concentration, whose acid dissociation constants in NaClO₄ 1 M at 25 °C were pK_HX = 3.9 ± 0.2, pK_HY = 7.5 ± 0.3, pK_HZ = 9.5 ± 0.2, respectively. With the proposed method the handling of alkaline HA solutions, the titration with very dilute NaOH or HCl solutions and the need for the availability of very small volumes of titrant to be added by microburettes may be avoided.     

Coulometric argentometric determination of microamounts of sulphur in iron and steel after reduction to hydrogen sulphide with iron(II) in strong phosphoric acid medium

A coulometric method was developed for the determination of microamounts of sulphur in iron and steel. Hydrogen sulphide is quantitatively evolved by reduction with iron(II) in strong phosphoric acid medium and is titrated with electrolytically generated silver ion from a silver anode. Microamounts of sulphide (2.96–224.3 μg) in sodium sulphide standard solutions could be determined with an error of only a few percent. Sulphur in a potassium sulphate standard solution is quantitatively reduced to hydrogen sulphide and could be separated from the solution by heating and determined accurately. Trace amounts of sulphur (7–100 μg g^?1) in iron and steels could be determined with a standard deviation of 0.7–2.1 μg g^?1.