Kinetic and spectral aspects in chemiluminescence system Eu(III)/HCO3/H2O2

Chemiluminescence (CL) of the systems containing Eu₂⁺ or HCO₃⁻ ions and hydrogen peroxide was studied. The kinetic curves and CL emission spectra of the systems were discussed. The emission spectrum of the system containing carbonates revealed two emission maxima: the first directly after initiation of the reaction by hydrogen peroxide and the second in several seconds after the first. On the basis of the characteristic bands in the CL spectrum the emitters in the system Eu₂⁺/HCO₃⁻/H₂O₂ were identified as: excited Eu³⁺ ions and excited products of carbonate decomposition. The emission bands for λ=600 and 420 nm appeared in a time distance of a few ten seconds.     

贵金属的化学发光分析

介绍化学发光分析的基本原理和测试技术,及其应用于测定贵金属的几种化学发光反应,并展望其前景。     

吐温80─H_2O_2化学发光新体系测定痕量lr（Ⅳ）

建立了吐温８０─Ｎ＿２Ｏ＿２体系测定痕量铱的新的化学发光分析法，方法的检测限为３．０×１０￣（－９）ｇ／ｍｌ；线性范围为１．０×１Ｏ￣（－８）～１．０×１０￣（－５）ｇ／ｍｌ；测定１００ｐｐｂ铱溶液的相对标准偏差为６．５％。     

—Review Paper—Current State-Of-The-Art Measurements Of Ozone In The Gas Phase And In Solution

This paper is a critical review and summary of the analytical procedures currently used by operating water utilities to control ozone treatment processes, considering disinfection as well as the many oxidative applications of ozone in water treatment applications. The role of common interferences in the various methods is described.

In operating U S., Canadian, European, and Japanese water treatment plants currently employing ozone as a primary disinfectant, ozone nearly always is followed by the addition of small quantities of chlorine, chlorine dioxide, or chloramine to provide the residual in the distribution system and to act as a secondary disinfectant. Clearly, the analytical procedures used must distinguish between the various species. This review critically presents these various factors and their implication with respect to “true values” of ozone determined under widely varying conditions.     

Comparison of Fourier,principal component and wavelet analyses for high speed flame measurements

The continuing advancement of high speed, combustion diagnostics calls for mathematical techniques that can extract key information from large datasets. This paper therefore describes a case study to compare the characterization of combustion dynamics behind a V-gutter flame holder using three mathematical methods: Fourier analysis, principal component analysis, (PCA), and wavelet analysis (WA). The comparison focuses on the analysis of the characteristic frequencies of flow–flame interactions, with a particular emphasis on the analysis of transient and unsteady combustion procedures, such as lean blow off. Experimental data obtained under a range of conditions were analyzed using all three methods, and several observations were made. When applied to the analysis of stable combustion processes, all three methods reported frequency characteristics that were similar both quantitatively and qualitatively. Under unstable and transient combustion conditions, the WA method is capable of revealing the dynamics of the frequency components in the measurements, while traditional Fourier and PCA methods encounter application restrictions. Lastly, these applications also demonstrated WA’s suitability for practical combustion measurements beyond chemiluminescence, such as its applicability to discrete signals, insensitivity to the choice of wavelet basis, and insensitivity to the target signal extracted from the raw measurements.     

石竹茶的营养成分分析及自由基清除作用

用化学发光法研究了石竹茶对活性氧自由基的清除作用及其影响因素,并对石竹茶的营养成分进行了分析。结果表明石竹茶具有良好的营养组成,且对O2-·、OH·及H2O2均有清除作用,其中对O2-的清除作用尤强。对同一种自由基,清除作用强弱的顺序依次为:第一次水提物〉第二次水提物〉第三次水提物〉第四次水提物。此外,清除自由基活性还与茶水放置时间成反比。结果提示石竹茶具有清除自由基、抗衰老功效,是一种良好的保健饮料。     

Influence of fuel composition on chemiluminescence emission in premixed flames of CH4/CO2/H2/CO blends

The growing concern about pollutant emissions and depletion of fossil fuels has been a strong motivator for the development of cleaner and more efficient combustion strategies, such as the gasification of coal, biomass or waste, which have increased the interest in using a new type of fuels, mainly composed of CH₄, H₂, CO and CO₂.These new fuels, commonly called syngas, display a wide range of compositions, which affects their combustion characteristics and, in some cases, are more prone to instabilities or flashback. Since flame properties have been demonstrated to be strongly related to equivalence ratio, a precise measurement of the flame stoichiometry is a key pre-requisite for combustion optimization and prevention of unstable regimes. In particular, chemiluminescence emission from flames has been largely tested for stoichiometry monitoring for methane flames, but its use in syngas flames has been far less studied. Consequently, the main goal of this work is analyzing the effect of fuel composition on the chemiluminescence vs. equivalence ratio curves for different fuel blends, as a first approach for a wide range of syngas compositions. The experimental results revealed that the ratio OH*/CH*, which had been widely demonstrated to be the best option for methane, may not be suitable for monitoring with certain fuels, such as those with a high percent of hydrogen. Alternatively, other signals, in particular the ratio OH*/CO₂*, appear as viable stoichiometry indicators in those cases.The analysis was also completed by numerical predictions with CHEMKIN. The comparisons of calculations with different flame models and experimental data reveals differences in the chemiluminescence vs. equivalence ratio curves for the different combustion regimes, depending on the range of the equivalence ratio ranges and fuel compositions. This finding, which confirms previous observations for a much narrower range of fuels, could have important practical consequences for the application of the technique in real combustors.     

一种新的产生和检测过氧亚硝基的化学发光体系

研究产生和消除过氧亚硝基（Peroxynitrite anion,ONOO^-）是自由基生物学和医学的一项紧迫任务。为此,建立了一种新的产生和检测ONOO^-的化学发光体系,并评估了检测的最佳条件。该方法为：10mmol／L羟胺与0．5mol,LNaOH、1mmol／L、乙二胺四乙酸二钠（Disodium ethylenediamine tetraacetate,EDTA）反应产生ONOO^-,随后用MnO2粉末过滤反应液以除去H2O2,然后在测量管内加入100μL抗氧化剂和860μL0．Imol／L的碳酸盐缓冲液（pH10）,再加入40μL过滤后的ONOO^-反应液、混匀、延迟10s,测10s化学发光强度。以抗氧化剂茶多酚、抗坏血酸、芦丁和黄芩苷作清除ONOO^-的实验。结果表明,本体系是一种灵敏价廉、可靠易行的筛选ONOO^-清除剂的新方法。     

Determination of propyl gallate in edible oil by high-performance liquid chromatography with chemiluminescence detection

A novel and convenient method based on high-performance liquid chromatography coupled with chemiluminescence (HPLC) for the determination of propyl gallate in edible oil is reported. The detection was based on the inhibition of chemiluminescence between luminol and hydrogen peroxide in alkaline solution. The analysis was performed using a C₁₈ column with isocratic 60:40 methanol/water. Under the optimum conditions, the concentration of propyl gallate was linear from 9?×?10^?6?mol?L^?1 to 1?×?10^?4?mol?L^?1 with a detection limit of 2?×?10^?7?mol?L^?1. The method is simple, sensitive, and inexpensive and was used for the determination of propyl gallate in edible oil.     

Spectroscopic and chemical-kinetic analysis of the phases of HCCI autoignition and combustion for single- and two-stage ignition fuels

The temporal phases of autoignition and combustion in an HCCI engine have been investigated in both an all-metal engine and a matching optical engine. Gasoline, a primary reference fuel mixture (PRF80), and several representative real-fuel constituents were examined. Only PRF80, which is a two-stage ignition fuel, exhibited a “cool-flame” low-temperature heat-release (LTHR) phase. For all fuels, slow exothermic reactions occurring at intermediate temperatures raised the charge temperature to the hot-ignition point. In addition to the amount of LTHR, differences in this intermediate-temperature heat-release (ITHR) phase affect the fuel ignition quality. Chemiluminescence images of iso-octane show a weak and uniform light emission during this phase. This is followed by the main high-temperature heat-release (HTHR) phase. Finally, a “burnout” phase was observed, with very weak uniform emission and near-zero heat-release rate (HRR). To better understand these combustion phases, chemiluminescence spectroscopy and chemical-kinetic analysis were applied for the single-stage ignition fuel, iso-octane, and the two-stage fuel, PRF80. For both fuels, the spectrum obtained during the ITHR phase was dominated by formaldehyde chemiluminescence. This was similar to the LTHR spectrum of PRF80, but the emission intensity and the temperature were much higher, indicating differences between the ITHR and LTHR phases. Chemical-kinetic modeling clarified the differences and similarities between the LTHR and ITHR phases and the cause of the enhanced ITHR with PRF80. The HTHR spectra for both fuels were dominated by a broad CO continuum with some contribution from bands of HCO, CH, and OH. The modeling showed that the CO+O→CO₂+hν reaction responsible for the CO continuum emission tracks the HTHR well, explaining the strong correlation observed experimentally between the total chemiluminescence and HRR during the HTHR phase. It also showed that the CO continuum does not contribute to the ITHR and LTHR chemiluminescence. Bands of H₂O and O₂ in the red and IR regions were also detected during the HTHR, which the data indicated were most likely due to thermal excitation. The very weak light emission in the “burnout” phase also appeared to be thermal emission from H₂O and O₂.