矿石中铈组稀土元素的测定——离子交换分离偶氮硝羧比色法

武汉大学合成了新显色剂——偶氮硝羧,并应用于矿石中铈组稀土元素的测定。我们研究了偶氮硝羧的显色反应,确定在2N醋酸介质中有利于抑制Sm的显色和消除钇组稀土元素的影响。为了地质工作适应在生产实际中的不同情况,我们制定了用离子交换和氨水沉淀分离干扰元素后,用偶氮硝羧比色测定矿石中铈组稀土(镧、铈、镨、钕)的方法,可作稀土总量(偶氮肿Ⅲ法)和铈组稀土(偶氮硝羧法)的连续测定。可测定矿石中0.01—0.1％铈组稀土元素,适用于独居石、磷钇矿、黑钨矿和离子吸附型稀土矿等不同类型矿石。生产第一线的地质队     

新显色剂二溴对甲基偶氮溴磺光度法测定铈组稀土的研究及应用

研究了新显色剂二溴对甲基偶氮溴磺与铈组稀土的显色反应,在０．６ｍｏｌ．Ｌ＾－１的盐酸介质中,试剂与铈组稀土元素形成２：１稳定的蓝色络合物,其最大吸收波长位于６４２ｎｍ处,稀土含在０－１．０μｇ／ｍＬ范围内符合比耳定律。建立了直接光度法测定钢铁样品中铈组稀土总量的方法。     

偶氮硝羧光度法测定矿石中铈组稀土元素

本文报导了偶氮硝羧的合成方法,研究了偶氮硝羧与稀土元素的显色反应,提出了不经分离,在钇组稀土存在下直接光度法测定铈组稀土(镧、铈、镨、钕)的新方法,并采用PMBP-苯萃取分离伴生元素,用偶氮肿Ⅲ光度法测定稀土总量,用偶氮硝羧光度法测定铈组稀土分量。可以测定矿石中0.0X—X％的稀土总量及铈组稀土分量,方法简便、快速、重现性好,适用于磷钇矿、独居石和吸附型稀土矿的分析。     

二溴硝基偶氮氯膦光度法直接测定土壤中铈组稀土元素

二溴硝基偶氮氯膦(DBNCPA)是一种性能优良的铈组稀土的灵敏显色剂,曾用于低合金钢、稀土球铁、镍基合金中的微量铈组稀土和玻璃中铈的测定.但土壤样品中铈组稀土的测定尚未见报道.本文主要研究了在盐酸介质中DBNCPA与铈的显色反应条件.发现反应能在高酸度条件下发生,而且反应灵敏度较高,摩尔吸光系数ε为1.1×10~5,许多常见离子几毫克乃至几十毫克都不干扰测定,可不经分离用光度法直接测定土壤中的铈组稀土元素.本法具有灵敏、准确、稳定、快速等特点,对七种不同土样的测定,均获得     

间三氟甲基偶氮氯膦(CPAmCF_3)与铀(Ⅵ)的显色反应研究及其应用

CPAmCF_3为新的不对称的偶氮氯膦型试剂。该试剂已用于钢铁中铈组稀土以及铁基和铝基合金中稀土总量的测定。除上述α型显色反应的研究和应用外,该试剂与稀土元素的β型显色反应亦已有报道,但未见用于铀的测定。本文研究了CFAmCF_3与铀的显色反应条件。该反应灵敏度高,为目前测定铀高灵敏度的方法之一。已用于铀矿样分析,结果较为满意。     

新显色剂二溴硝基偶氮氯膦的研究和应用 Ⅱ.光度法直接测定镍基合金中的铈组稀土

二溴硝基偶氮氯膦是一种新的稀土显色剂。该试剂在酸性溶液中为紫红色,与铈形成蓝绿色的配合物,配合比为3:1。试剂与铈组稀土的显色反应体系简单、显色酸度高、范围宽、不但灵敏度高,而且选择性好。应用于钇组稀土存在下测定镍基合金中的铈,结果令人满意。     

偶氮硝羧在光度法测定矿石中铈组稀土元素的应用

本文探讨了在甲酸介质中,稀土元素与偶氮硝羧的显色反应。选择EDTA(Na)作为抑制钇组稀土元素的络合剂,拟定了以PMBP萃取-甲酸反萃取稀土元素,连续测定稀土总量(偶氮胂Ⅲ光度法)和铈组稀土元素(偶氮硝羧光度法)的方法。本法比较准确,灵敏度高,选择性好。适用于独居石,磷钇矿,黑钨矿等不同类型矿石中0.01-1％铈族稀土元素(镧、铈、镨、钕等)的测定。实验部分 (一)仪器与主要试剂分光光度计(日本岛津QR50型)。铈组稀土元素标准溶液:根据三种类型稀土矿的光谱分析结果,配制了如下表所列的三种标准溶液。稀释每毫升相当于0.5毫克∑CeO_2的25％盐酸溶液,配制成每毫升相当于20微克∑CeO_2的25％盐酸     

稀土-漂蓝6B-邻菲罗啉-氯代十二烷基吡啶体系的分光光度性质及镧钇共存时钇的测定

多元络合物在分析化学中的应用提高了分析方法的灵敏度和选择性,为稀土元素的分组测定开辟了新途径。慈云祥研究了稀土-铬天青S-邻菲罗啉-溴代十六烷基三甲铵体系的显色反应,把混合配位体络合物和胶束增溶络合物统一在一个多元络合物体系中,具有较高的灵敏度和选择性,加入适当的竞争配位体可在铈组存在下测钇组稀土。Pande和Vekhancde分别研究了钇与漂蓝6B和溴化十六烷基三甲铵存在下钪、钇、镧与漂蓝6B的显色反应,表明漂蓝6B是一种有前途的显色     

铈和钛铁试剂显色反应机理的探讨及应用

本文研究了铈和钛铁试剂显色反应的机理。证实四价铈与钛铁试剂可瞬时形成紫红色的络合物。其最大吸收峰位于500nm,摩尔吸光系数为4.13×10~3。而三价铈只能和钛铁试剂形成无色络合物。但在碱性介质中,三价铈的无色络合物可被空气或溶液中的氧很快氧化为四价铈的有色络合物。据此可方便地测定铈或消除四价铈对导数吸收光谱法测定其它稀土元素时的谱带干扰。大量其它稀土元素及钍对铈的测定无干扰。本法可用于稀土氧化物中少量铈的测定。     

对马尿酸偶氮氯膦直接光度法测定钢铁中稀土总量的研究

对马尿酸偶氮氯膦是武汉大学最近合成的稀土新显色剂,其结构式为: 我们对该试剂与稀土元素显色反应条件和用于测定钢铁中稀土总量进行了研究。该试剂在0.02～0.5N各种酸介质中,均能与稀土元素立即反应生成兰色稳定络合物。络合物的最大吸收波长位于680nm左右。各稀土元素(La～Lu、Y)的络合物的摩尔吸光系数为(7.27～10.22)×10~4·1·mol~(-1)。cm~(-1)。该试剂的主要特点在于它与稀土元素反应具有显色酸度高、灵敏度较高。选择性和稳定性较好,允许共存元素量也较高。控制适当条件,它与铈和钇所形成的络合物的吸光度是一致的。所以它是一种目前测定稀土总量较为理想的试剂。即使有较大量EDTA、酒石酸以     

新4(或5)-取代不对称变色酸双偶氮胂酸型显色剂与稀土的显色反应研究

本文对二十一种新型的4(或5)-取代不对称变色酸双偶氮肿酸型显色剂与稀土的显色反应进行了研究,从中找出了一些结构与性能关系的规律,并筛选出性能优良的稀土显色剂。     

Synthesis of Fluoro-Contained Bisazo Chromotropic Acid Derivants and studies on Their Color Reactions with Rare Earth Elements

In this paper, a series of f1uoro-contained bisazo chromotropic acid derivants has been designed and synthesized. They are easily soluble in water, alcohol and acetone but insoluble in benzene, ether and chloroform. Some regularities of the effects of their molecular structure on the color reaction have also been studied. The result shows that in this series of reagents, DCF-chlorophosphonazo and DBF-chlorophosphonazo are excellent color reagents for the determination of the total amount of rare earth elements. The molar absor-ptivities of light and heavy rare earth elements are approach to each other. The tolerant quantity of Bi (Ⅲ) and Pb (Ⅱ) , Sn(Ⅳ) are larger than that of the other arsenazo or chlorophosphonazo type of color reagents. We also discover that p-fluorochlorophosphonazo can form β-type complexes with heavy rare earth elements, and p -fluoro-carboxyazo with light rare earth elements. If the reaction time is controlled, p -fluoro-carboxyao can form β-type complex only with La, and the     

The Spectrophotometric Determination of Sc in Eriochrome Canine R(Chrome azurol s)- Phosphatidl Choline System

Abstract

Eriochrome cyanine R(chrome azurol S) is used as a color reagent to determine Sc in the presence of phosphatidyl choline, σ = 3.7 × 10⁴ (4.5 × 10⁴). This method has been connected to extraction separation to determine Sc in the presence of rare earth elements, and good results have been obtained.

Phosphatidyl choline(PC) is a biochemical reagent, which can be used as a surfactant. It has been reported that chrome azurol S(CAS) can be used to determine Be in the presence of PC¹ but it has not been reported that eriochrome cyanine R(ECR) and CAS can be used to determine Sc in the presence of PC. This paper has put forward a method by which Sc can be determined. ECR (CAB) has been used as a color reagent and PC as a surfactant. Conditional experiments have been made and this method has been connected to extraction separation. Tributyl phosphate (TBP) extracts Sc from rare earth elements to make a determination and good results have been obtained.     

STUDIES ON THE SYNTHESES OF RARE EARTH COLOR REAGENTS OF POLY-HALOGENATED BISAZO TYPE AND THE RELATIONSHIP BETWEEN THEIR MOLECULAR STRUCTURES AND PROPERTIES

A sort of new rare earth color reagent-polyhalogenated bisazo chromotroplc acid derivants was designed and synthesized.They are easily soluble in water,alcohol and acetone,but insoluble in benzene,ethyl ether and chloroform.They are a kind of highly sensitive and excellently selective reagents for rare earth elements.The acidity of color reactions is strong (0.1N-4N) and the acidic range is wide.The relationship between the molecular structure and the reaction properties for rare earths was also studied.When the properties and positions of auxochromic groups are fixed,the sensitivities of reagents that have the complex functional groups-AsO3H2,-COOH and-PO3H2 are higher than others.     

Simultaneous spectrophotometric determination of thorium and rare earth metals with pyrimidine azo dyes and cetylpyridinium chloride

Thorium and rare earth elements (REE) react with 5-(2',4'-dimethylphenylazo)6-hydroxypyrimidine-2,4-dione (I) and 5-(4'-nitro-2',6'-dichlorophenylazo)6-hydroxypyrimidine-2,4-dione (II) in the absence of cetylpyridinium chloride (CPC) to form red complexes. The molar absorptivity and Sandell sensitivity were calculated in absence of CPC. In its presence, REE - complexes are not formed due to miceller masking, whereas Th(4+) has a sensitive reaction with the studied reagents I and II, with enhancement of the color intensity of the complex. Most of the foreign ions are tolerated in considerable amounts; 150-2400-fold amounts of rare earth do not interfere with the determination of thorium. The optimum experimental conditions of the complex formation reactions and the compositions of thorium complexes are described. A simple method is proposed for simultaneous determination of thorium and rare earth element without previous separation.     

多卤代变色酸双偶氮类稀土显色剂的合成及分子结构与吸光性能的关系

本文设计、合成了一类新型稀土显色剂--多卤代变色酸双偶氮衍生物,它们易溶于水、乙醇和丙酮,不溶于苯、己醚和氯仿,是具有高灵敏度、高选择性、显色酸度高、空白值低的优良稀土显色剂,本文还研究了试剂的分子结构和吸光性能的关系,当助色基及其取代位置一定时,具有-AsO₃H₂、-COOH、-PO_3H、-Cl络合功能基的性质,其灵敏度较高。     

Arsenazo III and its analogues-VII Colour reactions of the rare earth elements with a new reagent-carboxynitrazo

A new reagent, Carboxynitrazo, gives a colour reaction with some rare earth elements. For the individual rare earth elements the sensitivities of the reactions are very different. The difference is greatest for the elements of the Ce- and Y-subgroups. For the first subgroup the molar absorptivities are about 16 x 10(4) l.mole(-1) cm(-1), whereas most of the elements of the Y-group do not give any colour reaction. A possible procedure for the determination of lanthanum in the presence of ytterbium is discussed.     

Heavy Metals Make a Chain: A Catenated Bismuth Compound

Catenation is common for the light main-group elements whereas it is rare for the heavy elements. Herein, we report the first example of a neutral molecule containing a Bi₄ chain. It is prepared in a one-step reaction between bismuth trichloride and bis(diisopropylphosphino)amine in methanol suspension. The same reaction carried out in dichloromethane gives quite different products. All products have been characterized spectroscopically and using single-crystal X-ray analysis.     

Simultaneous determination of lanthanum and cerium in mixed rare earths with p-acetylarsenazo by spectrophotometry

A new method has been developed for the simultaneous spectrophotometric determination of small amounts of lanthanum and cerium in the presence of large amounts of rare earth elements. Lanthanum (III) and cerium (III) were determined spectrophotometrically with p-acetylarsenazo as the color reagent in the chloroacetic acid medium at pH 3.1 by measuring the absorbances of the complexes at 670 nm. The remained rare earths were masked with ethylenediaminetetracetic acid and ethylenediaminetetracetic acid-zinc during the analysis. The optimum conditions for the simultaneous determination of lanthanum and cerium have been defined. The individual content of lanthanum (III) and cerium (III) were determined by varying the amounts of EDTA and EDTA-Zn used in the analysis and solving the simultaneous absorbance equations based on the Beer's law. The proposed method has been successfully applied to the determination of lanthanum and cerium in Longnan mixed rare earth oxides and other heavy rare earths without preliminary separation with satisfactory results. The relative errors of all analytical results of the method were not more than 2% with good precision. The procedure does not require separation of lanthanum, cerium and the other rare earth elements.     

三溴偶氮胂与稀土元素显色反应研究(Ⅰ)——人发中痕量稀土元素的测定

人发中痕量稀土的分析对环境监测和职业病诊断、稀土微肥的推广应用具有重要意义。L.S.Chuang等曾用中子活化法和质谱分析法进行测定。迄今为止,还未见用分光光度法进行测定的报导。三溴偶氮胂[2-(2-胂酸基苯偶氮)-7-(2,4,6-三溴苯偶氮)-1。8-二羟基-3.6二磺酸萘](简称TBA)是一个优良的稀土总量试剂[摩尔吸光系