大量锆存在时微量钍的比色测定

本文叙述去氢抗坏血酸可以隐蔽锆与钍试剂的反应,并建议用于以钍试剂比色测定合锆溶液中的钍.最宜操作条件为酸度0.2-0.25N;加热时间一分半,钍试剂浓度为4毫克/50毫升.不同锆钍比例及不同去氢抗坏血酸量存在时均对钍的发色无影响.文中并叙述一快速测定独居石中钍的方法.     

新试剂偶氮硝膦-mN(NPA-mN)分光光度法测钍研究

钍的分光光度法已有综述报导,一般认为偶氮胂Ⅲ是测钍的良好显色剂。但是该试剂测钍时,锆、铀、钛等有严重干扰,往往需要经萃取分离,甚至经离子交换分离方能进行测定。近年来,又提出用偶氮胂M、偶氮胂-K。对乙酸基偶氮胂等试剂测定钍,这些试剂虽各有优点,但也都存在一定的局限性。本文研究了新试剂偶氮硝膦-mN〔3-(4-硝基-2-膦酸苯偶氮)-6-(3-硝基苯偶氮)-4,5-二羟基-2,7-萘二磺酸〕与钍的分光光度性能。NPA-mN与钍显色反应的特点是:操作简便,发色迅速,对比度大,发色酸度强,允许酸度范围宽,试剂与络合物均十分稳定,比尔定律     

应用氯化铵-酒石酸-铜铁试剂支持电解质示波极谱法测定矿石中钍

(一)方法提要本文研究了在氯化铵-酒石酸-铜铁试剂支持电解质中钍的极谱行为。在此介质中,钍波的峰电位可大大提前至-0.65～-0.75伏。在pH2～3左右,于试剂波后产生一清晰、良好的波。略经分离,可允许一定量铁、铜、铀、稀土、锆、锡、镓、铟、铌、钽、钛等存在。方法适应性广,重现性好,可用于不同试样中0.00X％-0.X％范围钍含量的测定。     

稀土络合滴定方法的改进—稀土合金中稀土总量的测定

稀土-硅、钙、镁合金中稀土总量的测定历来采用草酸盐重量法,手续繁杂,周期颇长。以后采用了络合滴定法,方法虽然简便,但由于与稀土共存的钍的干扰,使滴定终点不易判断而影响准确度。关于消除稀土络合滴定时钍的干扰,国内已有不少报导。例如首先将稀土和钍以氟化物或草酸盐形式沉淀分离,继则在一定的pH介质中以磷酸三丁酯-二甲苯,乙酰丙酮或铜试剂萃取分离钍。文献对含钍2％以上的样品采用六次甲     

钍试剂线扫极谱分析法测定蛋白质的研究

在0.2 mol/L pH 3.0的Britton-Robinson(B-R)缓冲溶液中,钍试剂于-0.49 V(vs.SCE)产生一个灵敏的线性扫描二阶导数极谱还原峰。当在上述溶液中加入人血清白蛋白(HSA)后,钍试剂在-0.49 V处的峰电流降低,而峰电位基本没有变化,这是由于HSA与钍试剂会发生结合反应,使溶液中游离的钍试剂浓度降低,相应的还原峰电流也降低。对结合反应条件和电化学测定条件进行了优化。在最佳条件下,峰电流的降低值同HSA的浓度在1.0~12.0 mg/L范围内呈线性关系。将本法应用于人血清样品的测定所得结果同考马斯亮蓝G-250光度法一致。此方法还可应用于牛血清白蛋白、卵清白蛋白等蛋白质的测定。     

对乙酰基偶氮胂分光光度法测定矿石中钍

在钍的分光光度法中,普遍采用以偶氮胂Ⅲ为代表的一类对称变色酸双偶氮型试剂。这类试剂虽然对钍有较高的灵敏度,然而选择性不很理想。对乙酰基偶氮胂[2-(2-胂酸基偶氮)-7-(4-乙酰基苯偶氮)-1,8-二羟基萘-3,6-二磺酸]是武汉大学化学系研制出的一种不对称双偶氮型试剂,具有比偶氮胂Ⅲ更好的光度特性,目前国内已开始在矿石中应用。本文就对乙酰基偶氮胂测定钍的条件,共存元素的干扰及消除方法进行了详细的试验。通过对比,     

鈹的分析化学Ⅰ.借对-磺基苯偶氮变色酸(SPADNS)比色测定鈹

許多偶氮染料能与铍在适宜的pH范围內生成有色化合物。如铍试剂Ⅱ,钍试剂,鈾试剂Ⅰ以及偶氮膦等已用于微量铍的测定。虽然对-磺基苯偶氮变色酸(SPADNS)在钍和锆的分光光度分析和螯合滴定中已有应用;并且等曾指出在碱性溶液中     

4-(H酸偶氮)-1-苯基-3-甲基吡唑啉酮与钍的显色反应及其应用

研究了新试剂4-(H酸偶氮)-1-苯基-3-甲基吡唑啉酮(HAPMP)与钍的显色反应.在pH=5.0的HAc-NaAc缓冲介质中,阳离子表面活性剂CFMAB存在下,HAPMP与Th(Ⅳ)反应生成2:1红色络合物,λ_(mas)=55nm,ε=2.24×10~5 L·mol~(-1)·cm~(-1).钍(Ⅳ)含量在0～640μg/L内符合比定律,方法用于合金中钍的测定,结果令人满意.     

矿石中微量钍的萃取比色测定——偶氮氯膦Ⅲ-十六烷基三甲基溴化铵分光光度法

目前,偶氮氯膦Ⅲ主要用于钍、铀等元素的分光光度法测定。偶氮氯膦Ⅲ同这些元素形成的络合物十分稳定,显色反应灵敏度很高,与四价钍生成有络色合物的克分子吸收系数达1.22×10~6。目前,矿石中钍的测定多用偶氮胂Ⅲ和钍试剂钍色法。本文提出利用长链铵,使偶氮氯膦Ⅲ与钍在其作用下,生成的紫蓝色三元络合物,用异戊醇-苯混合有机溶剂萃取该络合物,作钍的分光光度测定,试剂空白值小,灵敏度较高。同时制定了简易、快速的测定矿物岩石中微量钍的分析方法。     

岩石中微量钍的导数示波极谱测定(TBP-聚三氟氯乙烯反相色层分离富集)

钍的极谱测定过去报导很少,近年来国外有一些报导,Srefer选择0.01N硝酸锂作支持电解质测定微克量钍。Sindhu在0.1M NaClO_4和30％甲醇的乙酸缓冲溶液中(pH为4.8),有3-羟基吡啶-2-硫醇存在下测定20—40μM钍。Sugawara则采用Bi-EDTA取代法。Donoso介绍两种支持电解质中含有铀、钍的示波极谱测定。我们发现在0.025M柠檬酸,2×10~(-4)M铜铁试剂溶液中(PH为1—2),当有少量钍存在时,在铜铁试剂波之后,有一良好的导数示波极谱波,此波随着钍量增加而加大,灵敏度较高,可检测0.1ppm钍,     

Infrared Detection of Criegee Intermediates Formed during the Ozonolysis of β‐Pinene and Their Reactivity towards Sulfur Dioxide

Recently, direct kinetic experiments have shown that the oxidation of sulfur dioxide to sulfur trioxide by reaction with stabilized Criegee intermediates (CIs) is an important source of sulfuric acid in the atmosphere. So far, only small CIs, generated in photolysis experiments, have been directly detected. Herein, it is shown that large, stabilized CIs can be detected in the gas phase by FTIR spectroscopy during the ozonolysis of β‐pinene. Their transient absorption bands between 930 and 830 cm^?1 appear only in the initial phase of the ozonolysis reaction when the scavenging of stabilized CIs by the reaction products is slow. The large CIs react with sulfur dioxide to give sulfur trioxide and nopinone with a yield exceeding 80 %. Reactant consumption and product formation in time‐resolved β‐pinene ozonolysis experiments in the presence of sulfur dioxide have been kinetically modeled. The results suggest a fast reaction of sulfur dioxide with CIs arising from β‐pinene ozonolysis.     

一种用于食品中二氧化硫快速测定的样品前处理方法

提出了一种采用半微量蒸馏-半导体制冷技术的食品中二氧化硫快速提取的新方法, 研制出了可在15 min内完成二氧化硫提取的食品检测快速蒸馏提取装置. 采用本装置,  无需冷凝水和含汞吸收剂即可实现对样品中二氧化硫的蒸馏提取. 考察了蒸馏液酸度、   蒸馏液体积、 馏分收集体积和蒸馏提取时间对二氧化硫提取效率的影响. 研究结果表明,  采用该方法在30 min内即可完成对食品中二氧化硫的快速定量测定.     

催化发光法同时测定空气中的甲醛、苯和二氧化硫

基于甲醛、苯和二氧化硫在纳米Ti3CeY2O11上的催化发光有交叉敏感现象,在3个波长处分别确定甲醛、苯和二氧化硫浓度与催化发光信号强度的响应关系,再依据发光信号强度的叠加性特征即可获取甲醛、苯和二氧化硫的准确浓度,据此建立了同时测定空气中甲醛、苯和二氧化硫的新方法.3个分析波长分别为420、535和680 nm,敏感材料表面温度为280℃,载气流速为130 mL/min.本方法对甲醛、苯和二氧化硫的检出限(3σ)分别为0.04、0.05和0.10 mg/m3,线性范围分别为0.08~75.60 mg/m3、0.10~101.40 mg/m3和0.30~115.00 mg/m3, 回收率分别为96.4%~103.7%、97.8%~102.5%和97.2%~103.3%.常见共存物,如乙醛、甲苯、硫化氢、氨、甲醇、乙醇和二氧化碳等不干扰测定.连续200 h通浓度均为50 mg/m3的甲醛、苯和二氧化硫混合气体,发光强度的相对偏差≤2%,表明此纳米级复合氧化物对甲醛、苯和二氧化硫的敏感性的寿命长.本方法充分利用了交叉敏感现象,可以实现空气中甲醛、苯和二氧化硫的在线分析.     

Studies on photochemical reactions of air pollutants. XIV.Photooxidation of sulfur dioxide in air by various air pollutants

Upon exposure to sunlight, or to artificial light at wavelengths longer than 290 nm, sulfur dioxide in air underwent oxidation to give sulfur trioxide in the presence of air pollutants such as biacetyl (2,3-butanedione), benzaldehyde and nitrogen dioxide, but not in their absence. Only nitrogen dioxide completely oxidized sulfur dioxide to sulfur trioxide.     

Simple spectrophotometry method for the determination of sulfur dioxide in an alcohol-thionyl chloride reaction

Thionyl chloride is often used to convert alcohols into more reactive alkyl chloride, which can be easily converted to many compounds that are not possible from alcohols directly. One important reaction of alkyl chloride is nucleophilic substitution, which is typically conducted under basic conditions. Sulfur dioxide, the by-product from alcohol-thionyl chloride reactions, often reacts with alkyl chloride to form a sulfonyl acid impurity, resulting in yield loss. Therefore, the alkyl chloride is typically isolated to remove the by-products including sulfur dioxide. However, in our laboratory, the alkyl chloride formed from alcohol and thionyl chloride was found to be a potential mutagenic impurity, and isolation of this compound would require extensive safety measures. As a result, a flow-through process was developed, and the sulfur dioxide was purged using a combination of vacuum degassing and nitrogen gas sweeping. An analytical method that can quickly and accurately quantitate residual levels of sulfur dioxide in the reaction mixture is desired for in-process monitoring. We report here a simple ultraviolet (UV) spectrophotometry method for this measurement.     

Solubilities of volatile solutes in poly(vinyl acetate) from 125 to 200°C

Gas-liquid chromatography (GLC) was used to measure Henry's law constants for ethylene, ethane, carbon dioxide, sulfur dioxide, methyl chloride, vinyl acetate, isopropyl alcohol, methyl ethyl ketone, and acetone in liquid poly(vinyl acetate) in the region 125 to 200°C. Retention-time differences were measured relative to nitrogen and corrections for nitrogen's finite solubility were applied; these corrections are significant when measuring the solubilities of sparingly soluble solutes by the GLC method. The effect of GLC column diameter is discussed.     

Continuous Monitoring of Sulfur Dioxide with a Gas Permeation Denuder-Based System

 This study describes a continuous flow procedure for monitoring atmospheric sulfur dioxide using a planar gas permeation denuder (GPD) and a fiber optic spectrometer. When gaseous samples are directed through a GPD which consists of a gas-permeable membrane of poly(vinylidene) difluoride and two perspex blocks with engraved channels of mirror image, the fraction of sulfur dioxide passing the membrane is absorbed in a flowing stream of 5.0×10⁻⁴ mol L⁻¹ 5,5′-dithiobis(2,2′-dinitrobenzoic acid) (DTNB) in 0.025 mol L⁻¹ phosphate buffer of pH 7.0, and reacts with DTNB to yield a yellow product. This product is monitored spectrophotometrically at 410 nm with a miniature charge-coupled device (CCD) fiber optic spectrometer. The analytical range of sulfur dioxide is easily adjusted via the flow rate of DTNB solution, normally from 200 ppb to 94 ppm (v/v). The procedure is hardly interfered with by coexisting metal and non-metal species, except for hydrogen sulfide in the atmosphere. The error caused by hydrogen sulfide at a sulfur dioxide level (in ppm) of 2% is less than ±10%. With the proposed procedure, the result for a mimetic air sample is very close to that of the ultraviolet fluorescence method. Correspondence: College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China. e-mail: yli@chem.pku.edu.cn Received August 12, 2002; accepted November 9, 2002     

Assay of Sulfur in Organic Liquids Using a Mercury Displacement Method

Abstract

A method for the assay of sulfur in organic liquids is presented. The method utilizes an oxidative combustion process coupled with a piezoelectric crystal detector. The sulfur dioxide evolved upon combustion of the organic liquid is bubbled through a mercurous nitrate solution. The mercury vapor produced is detected by a piezoelectric crystal due to the formation of a mercury amalgam.     

气相色谱法测定合成气中硫化合物

建立了气相色谱法测定合成气中硫化合物的方法。采用能自动进样的六通阀和对硫磷有选择性的FPD检测器,色谱峰面积与硫化合物含量存在很好的双对数线性关系。对H2S,COS及CS2三种气体的线性相关系数依次为0．9995,0．9997及0．9997。     

通氮燃烧碘量法测定锰铁及硅铁中硫

提出氮气气氛中以CuO SiO2作添加剂进行燃烧碘量法测定硅铁及锰铁中的硫,克服了通氧燃烧时硫的回收率低且波动大的缺点,采用这一新方法,试样中硫的回收率接近100％,因此使方法的准确度和精密度显著提高。